JP6853086B2 - Aromatic compounds and methods for producing them - Google Patents
Aromatic compounds and methods for producing them Download PDFInfo
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- JP6853086B2 JP6853086B2 JP2017061738A JP2017061738A JP6853086B2 JP 6853086 B2 JP6853086 B2 JP 6853086B2 JP 2017061738 A JP2017061738 A JP 2017061738A JP 2017061738 A JP2017061738 A JP 2017061738A JP 6853086 B2 JP6853086 B2 JP 6853086B2
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- 150000001491 aromatic compounds Chemical class 0.000 title claims description 22
- 238000000034 method Methods 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims description 29
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 description 22
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- -1 aromatic ester compound Chemical class 0.000 description 9
- 125000005978 1-naphthyloxy group Chemical group 0.000 description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 0 C*1=CC=**C1 Chemical compound C*1=CC=**C1 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229940069428 antacid Drugs 0.000 description 2
- 239000003159 antacid agent Substances 0.000 description 2
- 230000001458 anti-acid effect Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- OVXKCRNZYALQSS-UHFFFAOYSA-N naphthalen-1-yl 4-hydroxybenzoate Chemical compound C1=CC(O)=CC=C1C(=O)OC1=CC=CC2=CC=CC=C12 OVXKCRNZYALQSS-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N O=C(c(cc1)ccc1C(Cl)=O)Cl Chemical compound O=C(c(cc1)ccc1C(Cl)=O)Cl LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N O=C(c1cc(C(Cl)=O)ccc1)Cl Chemical compound O=C(c1cc(C(Cl)=O)ccc1)Cl FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N acetaldehyde dimethyl acetal Natural products COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052717 sulfur Chemical group 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Description
本発明は、新規な芳香族化合物およびその製造方法に関する。 The present invention relates to a novel aromatic compound and a method for producing the same.
複数の芳香族基がエステル結合してなる芳香族エステル化合物は、感熱記録材料（特許文献１）、光学材料（特許文献２、特許文献３）、トナー材料（特許文献４）等の各種材料やポリマー合成触媒（特許文献５）など、幅広い用途への使用が提案されている。
このような芳香族化合物としては、芳香族基が３個以下の比較的低分子のものや、フェニル基のみからなるものが知られているが、フェニル基およびナフチル基の両方の芳香族基を４〜１０個有する芳香族化合物については未だ知られていない。
The aromatic ester compound in which a plurality of aromatic groups are ester-bonded includes various materials such as a heat-sensitive recording material (Patent Document 1), an optical material (Patent Document 2 and Patent Document 3), and a toner material (Patent Document 4). It has been proposed to be used in a wide range of applications such as polymer synthesis catalysts (Patent Document 5).
As such aromatic compounds, those having a relatively low molecular weight of 3 or less aromatic groups and those consisting of only a phenyl group are known, but both aromatic groups of a phenyl group and a naphthyl group are used. Nothing is known about aromatic compounds having 4 to 10 groups.
本発明の目的は、感熱記録材料、光学材料、トナー材料等の各種材料やポリマー合成触媒として有用な、新規な芳香族化合物を提供することにある。また、本発明の他の目的は新規な芳香族化合物の製造方法を提供することにある。 An object of the present invention is to provide various materials such as heat-sensitive recording materials, optical materials, toner materials, and novel aromatic compounds useful as polymer synthesis catalysts. Another object of the present invention is to provide a novel method for producing an aromatic compound.
本発明は、式（１）で表される芳香族化合物に関する。
また、本発明は式（２）で表される化合物と式（３）で表される化合物を反応させる工程を含む、式（１）で表される芳香族化合物の製造方法に関する。
本発明の芳香族化合物は、感熱記録材料、光学材料、トナー材料等の各種材料やポリマー合成触媒として使用できる。 The aromatic compound of the present invention can be used as various materials such as a heat-sensitive recording material, an optical material, and a toner material, and as a polymer synthesis catalyst.
本発明は、式（１）で表される芳香族化合物である。
本発明の好ましい態様において、式（１）で表される化合物としては、下記式（１）−１〜（１）−３で表される化合物が挙げられる。
式（１）中のＡｒ１で表される２価の芳香族基としては、例えば下記式（ａ）〜（ｆ）で表される基が挙げられる。式（ａ）〜（ｆ）において、「※」は、それぞれ、エステルとの結合位置を表す。 Examples of the divalent aromatic group represented by Ar 1 in the formula (1) include groups represented by the following formulas (a) to (f). In the formulas (a) to (f), "*" represents the bonding position with the ester, respectively.
式（１）中のＡｒ２で表される１価の芳香族基としては、例えば下記式（ｇ）〜（ｉ）で表される基が挙げられる。式（ｇ）〜（ｉ）において、「※」は、それぞれ、エステルとの結合位置を表す。 Examples of the monovalent aromatic group represented by Ar 2 in the formula (1) include groups represented by the following formulas (g) to (i). In the formulas (g) to (i), "*" represents the bonding position with the ester, respectively.
これらの芳香族基は、環内に、窒素原子、酸素原子、および硫黄原子等のヘテロ原子を含んでいてもよい。すなわち、これらの芳香族基は、複素環であってもよい。 These aromatic groups may contain heteroatoms such as nitrogen atom, oxygen atom, and sulfur atom in the ring. That is, these aromatic groups may be heterocycles.
本発明の芳香族化合物の好ましい態様において、式（１）中のＡｒ１は上記式（ａ）で表される基であり、Ａｒ２は上記式（ｈ）で表される基であり、すなわち、式（１）で表される化合物としては、式（４）で表される化合物（イソフタル酸ジ−４−［（１−ナフチルオキシ）カルボニル］フェニルエステル）である。
本発明の式（１）で表される芳香族化合物の製造方法は、例えば式（２）で表される化合物と式（３）で表される化合物を反応させる工程を含む製造方法である。
２価および１価の芳香族基は、前述のものと同じものである。 The divalent and monovalent aromatic groups are the same as those described above.
式（３）で表される化合物としては、例えば下記式（３）−１〜（３）−３で表される化合物が挙げられる。下記式（３）−１〜（３）−３中の塩素原子の一部または全ては、臭素原子で置換されていてもよい。 Examples of the compound represented by the formula (3) include compounds represented by the following formulas (3) -1 to (3) -3. Some or all of the chlorine atoms in the following formulas (3) -1 to (3) -3 may be substituted with bromine atoms.
式（２）で表される化合物および式（３）で表される化合物としては、市販のものや、当業者に知られた方法で製造したものを用いることができる。 As the compound represented by the formula (2) and the compound represented by the formula (3), a commercially available compound or a compound produced by a method known to those skilled in the art can be used.
本発明の式（１）で表される芳香族化合物の製造方法は、式（２）で表される化合物および式（３）で表される化合物を、脱酸剤および溶媒の存在下で作用させることにより実施してもよい。 In the method for producing an aromatic compound represented by the formula (1) of the present invention, the compound represented by the formula (2) and the compound represented by the formula (3) are acted on in the presence of a deoxidizer and a solvent. It may be carried out by letting.
脱酸剤としては、炭酸水素ナトリウム、炭酸ナトリウム、炭酸カリウム、ピリジンおよびトリエチルアミンからなる群から選択される一種以上が挙げられる。 Examples of the antacid include one or more selected from the group consisting of sodium hydrogen carbonate, sodium carbonate, potassium carbonate, pyridine and triethylamine.
脱酸剤の使用量としては、特に限定されないが、通常、原料である式（２）で表される化合物１モル当量に対して０．６〜１．５モル当量が好ましい。 The amount of the deoxidizer used is not particularly limited, but is usually preferably 0.6 to 1.5 molar equivalents with respect to 1 molar equivalent of the compound represented by the formula (2), which is a raw material.
溶媒としては、テトラヒドロフラン、ＤＭＦ、ＤＭＡ、メタノール、エタノール、イソプロパノール、アセトン、ジエチルエーテル、クロロベンゼン、ヘキサン、ヘプタン、デカン、ニトロベンゼン、二硫化炭素、ニトロメタン、ジクロロメタン、ジクロロエタン、テトラヒドロフラン、ジオキサン、ベンゼン、トルエン、キシレン、四塩化炭素、ニトロメタン、アセトニトリルおよび軽油からなる群から選択される一種以上が挙げられ、反応性に優れる点でテトラヒドロフランが好ましい。 Solvents include tetrahydrofuran, DMF, DMA, methanol, ethanol, isopropanol, acetone, diethyl ether, chlorobenzene, hexane, heptane, decane, nitrobenzene, carbon disulfide, nitromethane, dichloromethane, dichloroethane, tetrahydrofuran, dioxane, benzene, toluene, xylene. , One or more selected from the group consisting of carbon tetrachloride, nitromethane, acetonitrile and light oil, and tetrahydrofuran is preferable in terms of excellent reactivity.
溶媒の使用量としては、特に限定されないが、通常、原料である式（２）で表される化合物１００重量部に対して２００〜６００重量部であるのが好ましい。 The amount of the solvent used is not particularly limited, but is usually preferably 200 to 600 parts by weight with respect to 100 parts by weight of the compound represented by the formula (2) as a raw material.
式（２）で表される化合物は、式（３）で表される化合物１モル当量に対して１．８〜３モル当量存在させて反応することが好ましく、１．９〜２．５モル当量存在させて反応することがより好ましい。式（２）で表される化合物が式（３）で表される化合物１モル当量に対して１．８モル当量未満である場合、反応が十分に進行しない傾向があり、式（２）で表される化合物が式（３）で表される化合物１モル当量に対して３モル当量を超過する場合、原料の無駄が多く、副生物が生成する傾向がある。 The compound represented by the formula (2) is preferably reacted in the presence of 1.8 to 3 molar equivalents with respect to 1 molar equivalent of the compound represented by the formula (3). It is more preferable to react in the presence of an equivalent amount. When the compound represented by the formula (2) is less than 1.8 molar equivalents with respect to 1 molar equivalent of the compound represented by the formula (3), the reaction tends not to proceed sufficiently, and the formula (2) When the represented compound exceeds 3 molar equivalents with respect to 1 molar equivalent of the compound represented by the formula (3), the raw material is wasted and by-products tend to be produced.
反応温度は原料や溶媒などによって異なるため、特に限定されないが、通常５０〜１５０℃で行われ、好ましくは用いる溶媒の沸点近傍温度で還流しながら反応を実施するのがよい。 Since the reaction temperature varies depending on the raw material, solvent and the like, it is not particularly limited, but it is usually carried out at 50 to 150 ° C., and it is preferable to carry out the reaction while refluxing at a temperature near the boiling point of the solvent to be used.
反応時間は原料や溶媒などによって異なるため、特に限定されないが、通常２〜１５時間行われる。 The reaction time varies depending on the raw material, solvent, etc., and is not particularly limited, but is usually 2 to 15 hours.
反応後、得られた芳香族化合物は、精製によって純度を向上させることができる。精製は、濾過、洗浄、濃縮、抽出、蒸留、カラムクロマト分離等の一般的な精製操作を経て、適宜目的とする純度まで精製することができる。 After the reaction, the obtained aromatic compound can be purified to improve its purity. Purification can be carried out to a desired purity as appropriate through general purification operations such as filtration, washing, concentration, extraction, distillation, and column chromatographic separation.
式（４）で表されるイソフタル酸ジ−４−［（１−ナフチルオキシ）カルボニル］フェニルエステルの製造方法は、例えば式（５）で表される４−ヒドロキシ安息香酸１−ナフチルエステルと式（６）で表されるイソフタノイルクロライドを反応させる工程を含む製造方法が挙げられる。
式（４）で表されるイソフタル酸ジ−４−［（１−ナフチルオキシ）カルボニル］フェニルエステルの製造方法において、前述の脱酸剤や溶媒を使用してよく、同様の反応条件を適用してよい。 In the method for producing the isophthalic acid di-4-[(1-naphthyloxy) carbonyl] phenyl ester represented by the formula (4), the above-mentioned antacid or solvent may be used, and the same reaction conditions are applied. It's okay.
このようにして得られた式（１）で表される芳香族化合物は、感熱記録材料、光学材料、トナー材料等の各種材料やポリマー合成触媒として有用である。 The aromatic compound represented by the formula (1) thus obtained is useful as various materials such as a heat-sensitive recording material, an optical material, and a toner material, and as a polymer synthesis catalyst.
また、式（１）で表される芳香族化合物は、樹脂の特性、例えば耐熱性、機械特性、熱特性（熱伝導性、放熱性等）、ガスバリア性、光学特性、および流動性等を改質できる、樹脂用の改質剤として利用し得る。 Further, the aromatic compound represented by the formula (1) has modified resin properties such as heat resistance, mechanical properties, thermal properties (thermal conductivity, heat dissipation, etc.), gas barrier properties, optical properties, fluidity, and the like. It can be used as a quality modifier for resins.
以下に実施例を挙げて本発明をより具体的に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
各化合物は以下の分析方法によって分析した。 Each compound was analyzed by the following analytical method.
＜１Ｈ−ＮＭＲスペクトル＞
サンプル１０ｍｇを重水素化ジメチルスルホキシドで溶解し、Ｂｒｕｋｅｒ Ｂｉｏｓｐｉｎ ＡＶ４００Ｍ（Ｂｒｕｋｅｒ社製）を用いて、溶液状態での１Ｈ−ＮＭＲスペクトルを測定した。
< 1 1 H-NMR spectrum>
10 mg of the sample was dissolved in deuterated dimethyl sulfoxide, and 1 H-NMR spectrum in a solution state was measured using Bruker Biospin AV400M (manufactured by Bruker).
＜ＦＴ−ＩＲスペクトル＞
Ｓｐｅｃｔｒｕｍ Ｏｎｅ（ＰｅｒｋｉｎＥｌｍｅｒ社製）を用いてＦＴ−ＩＲスペクトルを測定した。
<FT-IR spectrum>
The FT-IR spectrum was measured using Spectrum One (manufactured by PerkinElmer).
＜ＭＳスペクトル＞
Ｗａｔｅｒｓ ２６９０／２９９６ Ａｌｌｉａｎｃｅ−ＴＱ Ｄｅｔｅｃｔｏｒを用いてＭＳスペクトルを測定した。
<MS spectrum>
MS spectra were measured using Waters 2690/2996 Alliance-TQ Detector.
＜高速液体クロマトグラフィー（ＨＰＬＣ）＞
装置： Ｗａｔｅｒｓ アライアンス ２６９０／２９９６
カラム型番： Ｌ−Ｃｏｌｕｍｎ
液量： １．０ｍＬ／分
溶媒比： Ｈ２Ｏ（ｐＨ２．３）／ＣＨ３ＯＨ＝６７／３３（４分）→２分→３０／７０（２４分）→１０／９０（２９分）、グラジエント分析
波長： ２２０ｎｍ
カラム温度： ４０℃
尚、イソフタル酸ジ−４−［（１−ナフチルオキシ）カルボニル］フェニルエステルの純度は、ＨＰＬＣチャートの面積％から算出した。
<High Performance Liquid Chromatography (HPLC)>
Equipment: Waters Alliance 2690/2996
Column model number: L-Column
Liquid volume: 1.0 mL / min Solvent ratio: H 2 O (pH 2.3) / CH 3 OH = 67/33 (4 minutes) → 2 minutes → 30/70 (24 minutes) → 10/90 (29 minutes) , Gradient analysis Wavelength: 220nm
Column temperature: 40 ° C
The purity of the isophthalic acid di-4-[(1-naphthyloxy) carbonyl] phenyl ester was calculated from the area% of the HPLC chart.
実施例１
撹拌機、温度センサーおよび還流管を備えた５００ｍＬの４口フラスコに、４−ヒドロキシ安息香酸１−ナフチルエステル６５．１ｇ（０．２５ｍｏｌ）およびテトラヒドロフラン２６０ｇを加えて、窒素気流下、室温で撹拌し溶解させた。そこにイソフタノイルクロライド２５ｇ（０．１２ｍｏｌ）およびピリジン２０．５ｇ（０．２６ｍｏｌ）をさらに加えて、窒素気流下、撹拌しながら６６℃まで昇温し、同温度で８時間還流した。撹拌終了後、反応液を室温まで冷却し、得られた固形物を濾別し、テトラヒドロフラン１３０ｇで洗浄した。得られた固形物を水２６０ｇで懸濁洗浄し、濾別によって固形物を取り出した。
Example 1
To a 500 mL four-necked flask equipped with a stirrer, a temperature sensor and a reflux tube, 65.1 g (0.25 mol) of 4-hydroxybenzoic acid 1-naphthyl ester and 260 g of tetrahydrofuran were added and stirred at room temperature under a nitrogen stream. It was dissolved. 25 g (0.12 mol) of isophthalnoyl chloride and 20.5 g (0.26 mol) of pyridine were further added thereto, the temperature was raised to 66 ° C. with stirring under a nitrogen stream, and the mixture was refluxed at the same temperature for 8 hours. After completion of stirring, the reaction solution was cooled to room temperature, the obtained solid was filtered off, and washed with 130 g of tetrahydrofuran. The obtained solid was suspended and washed with 260 g of water, and the solid was taken out by filtration.
得られた固形物を水１３０ｇで洗浄した後、７０℃、１０Ｔｏｒｒの条件で乾燥させて、イソフタル酸ジ−４−［（１−ナフチルオキシ）カルボニル］フェニルエステルの結晶５２．３ｇを得た（収率６４．５ｍｏｌ％、純度９７．８％）。 The obtained solid was washed with 130 g of water and then dried under the conditions of 70 ° C. and 10 Torr to obtain 52.3 g of crystals of isophthalic acid di-4-[(1-naphthyloxy) carbonyl] phenyl ester (). Yield 64.5 mol%, purity 97.8%).
得られたイソフタル酸ジ−４−［（１−ナフチルオキシ）カルボニル］フェニルエステルの結晶について１Ｈ−ＮＭＲスペクトル、ＦＴ−ＩＲスペクトルおよびＭＳスペクトルを測定した。１Ｈ−ＮＭＲスペクトルを図１に、ＦＴ−ＩＲスペクトルを図２に示す。また、１Ｈ−ＮＭＲスペクトル、ＦＴ−ＩＲスペクトルおよびＭＳスペクトルの帰属を下記に示す。 1 H-NMR spectrum, FT-IR spectrum and MS spectrum were measured for the obtained crystals of isophthalic acid di-4-[(1-naphthyloxy) carbonyl] phenyl ester. 1 The 1 H-NMR spectrum is shown in FIG. 1 and the FT-IR spectrum is shown in FIG. In addition, the attribution of 1 H-NMR spectrum, FT-IR spectrum and MS spectrum is shown below.
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＤＭＳＯ−ｄ６）：δ８．８９（ｓ，１Ｈ，Ｈｋ），８．５７（ｄｄ，２Ｈ，Ｈｊ，Ｊ＝８．０，２．０Ｈｚ），８．４２（ｄ，４Ｈ，Ｈｈ，８．０Ｈｚ），８．０６（ｄｄ，２Ｈ，Ｈａ，Ｊ＝８．０，２．０Ｈｚ），７．９５−７．９０（ｍ，５Ｈ，Ｈｄ Ｈｅ Ｈｌ），７．６９（ｄ，４Ｈ，Ｈｉ，Ｊ＝８．０Ｈｚ），７．６４−７．５８（ｍ，６Ｈ，Ｈｂ Ｈｃ Ｈｆ），７．５２（ｄ，２Ｈ，Ｈｇ，Ｊ＝８．０Ｈｚ）
ＦＴ−ＩＲ：１７３８ｃｍ−１（Ｃ＝Ｏ伸縮）、３０５９ｃｍ−１（Ｃ−Ｈ伸縮）
ＭＳ：ｍ／ｚ＝６５９[Ｍ＋Ｈ]＋
本発明の好ましい態様は以下を包含する。
〔１〕式（１）で表される芳香族化合物。
［化１］
〔２〕Ａｒ １ は以下の式（ａ）〜（ｆ）：
［化２］
のいずれかで表される基であり、Ａｒ ２ は以下の式（ｇ）〜（ｉ）：
［化３］
のいずれかで表される基である、〔１〕に記載の芳香族化合物。
〔３〕Ａｒ １ は式（ａ）で表される基であり、Ａｒ ２ は式（ｈ）で表される基である、〔２〕に記載の芳香族化合物。
〔４〕式（２）で表される化合物と式（３）で表される化合物を反応させる工程を含む、〔１〕〜〔３〕のいずれかに記載の芳香族化合物の製造方法。
［化４］
FT-IR: 1738 cm -1 (C = O expansion and contraction), 3059 cm -1 (CH expansion and contraction)
MS: m / z = 659 [M + H] +
Preferred embodiments of the present invention include:
[1] An aromatic compound represented by the formula (1).
[Chemical 1]
[2] Ar 1 has the following equations (a) to (f):
[Chemical 2]
Ar 2 is a group represented by any of the following formulas (g) to (i):
[Chemical 3]
The aromatic compound according to [1], which is a group represented by any of the above.
[3] The aromatic compound according to [2], wherein Ar 1 is a group represented by the formula (a) and Ar 2 is a group represented by the formula (h).
[4] The method for producing an aromatic compound according to any one of [1] to [3], which comprises a step of reacting a compound represented by the formula (2) with a compound represented by the formula (3).
[Chemical 4]
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