JP5834390B2 - Method for producing diacyl derivative - Google Patents
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- JP5834390B2 JP5834390B2 JP2010225471A JP2010225471A JP5834390B2 JP 5834390 B2 JP5834390 B2 JP 5834390B2 JP 2010225471 A JP2010225471 A JP 2010225471A JP 2010225471 A JP2010225471 A JP 2010225471A JP 5834390 B2 JP5834390 B2 JP 5834390B2
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- 238000004519 manufacturing process Methods 0.000 title claims description 18
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 14
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 10
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 125000004434 sulfur atom Chemical group 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 6
- 150000003672 ureas Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- -1 chlorine ions Chemical class 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 4
- 229920003235 aromatic polyamide Polymers 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000004760 aramid Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- UOFDVLCOMURSTA-UHFFFAOYSA-N 2-(2-carboxyphenoxy)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1OC1=CC=CC=C1C(O)=O UOFDVLCOMURSTA-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- OSUWBBMPVXVSOA-UHFFFAOYSA-N 4-(4-carbonochloridoylphenoxy)benzoyl chloride Chemical compound C1=CC(C(=O)Cl)=CC=C1OC1=CC=C(C(Cl)=O)C=C1 OSUWBBMPVXVSOA-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- AOFRNZNXMCOXHP-UHFFFAOYSA-N 2-(2-carboxyphenyl)sulfonylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1C(O)=O AOFRNZNXMCOXHP-UHFFFAOYSA-N 0.000 description 1
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 description 1
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- PCWKTVQPSYMIJT-UHFFFAOYSA-N O(C1=CC=C(C(=O)O)C=C1)C1(C(=O)O)CC=CC=C1 Chemical compound O(C1=CC=C(C(=O)O)C=C1)C1(C(=O)O)CC=CC=C1 PCWKTVQPSYMIJT-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical group C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- XMFCLBUQBWFZBP-UHFFFAOYSA-N bis(2-methylimidazol-1-yl)methanone Chemical compound CC1=NC=CN1C(=O)N1C(C)=NC=C1 XMFCLBUQBWFZBP-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920002577 polybenzoxazole Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Description
本発明は、ジアシル誘導体の新規な製造方法に関するものである。 The present invention relates to a novel method for producing a diacyl derivative.
従来、耐熱性、高強度のポリマーとして全芳香環ポリアミド、アラミドが知られている。全芳香環ポリアミドの製造方法として、一般的にはジカルボン酸の塩化物とジアミンを重合する脱塩酸反応を用いる方法が知られている。しかしながら、ジカルボン酸の塩化物を用いて、全芳香環ポリアミドを製造する場合、得られるポリマーに塩素イオンが混入し、電子部品の腐食の原因となることがある。このため、ジカルボン酸の塩化物から製造した全芳香環ポリアミドは、半導体素子の保護膜、再配線膜、ディスプレーの絶縁膜など電気絶縁性が要求される用途には適用できない。 Conventionally, wholly aromatic polyamides and aramids are known as heat-resistant and high-strength polymers. As a method for producing a wholly aromatic ring polyamide, a method using a dehydrochlorination reaction for polymerizing a dicarboxylic acid chloride and a diamine is generally known. However, when a wholly aromatic polyamide is produced using a dicarboxylic acid chloride, chlorine ions may be mixed into the resulting polymer, which may cause corrosion of electronic components. For this reason, wholly aromatic polyamides produced from dicarboxylic acid chlorides cannot be applied to applications requiring electrical insulation, such as protective films for semiconductor elements, rewiring films, and insulating films for displays.
そこで、全芳香環ポリアミドの製造方法として、ジカルボン酸の活性エステルを用いる方法が考案された。例えば、特許文献１では、縮合剤としてカルボジイミド化合物を用いて、ジカルボン酸とヒドロキシベンゾトリアゾールを反応させて活性エステルを得る方法が報告されている。しかしながら、この方法では得られた活性エステルに、カルボジイミドが反応してできたウレア化合物が付着し、高純度の活性エステルを得ることができない。 Thus, a method of using an active ester of a dicarboxylic acid has been devised as a method for producing a wholly aromatic ring polyamide. For example, Patent Document 1 reports a method of obtaining an active ester by reacting a dicarboxylic acid and hydroxybenzotriazole using a carbodiimide compound as a condensing agent. However, in this method, a urea compound formed by the reaction of carbodiimide adheres to the obtained active ester, and a high-purity active ester cannot be obtained.
一方、全芳香環ポリアミドの製造方法として、ジカルボン酸の活性アミドを使用する方法があり、ジカルボン酸の活性アミドとして、ジイミダゾリド化合物の合成方法が開示されている（例えば、特許文献２、３、非特許文献１参照）。しかしながら、この方法では、ジカルボン酸の塩化物とイミダゾールを反応させており、得られたジイミダゾリド化合物に塩素イオンが含まれる恐れがある。また、この方法では最初にジカルボン酸をジカルボン酸の塩化物に導き、次いでイミダゾールを反応させるという２段階で合成されており、反応工程が長く、総合収率が低いという欠点がある。 On the other hand, as a method for producing a wholly aromatic ring polyamide, there is a method using an active amide of a dicarboxylic acid, and a method for synthesizing a diimidazolide compound is disclosed as an active amide of a dicarboxylic acid (for example, Patent Documents 2, 3, Patent Document 1). However, in this method, chloride of dicarboxylic acid is reacted with imidazole, and the resulting diimidazolide compound may contain chloride ions. In addition, this method is synthesized in two steps: firstly dicarboxylic acid is converted to dicarboxylic acid chloride and then reacted with imidazole, which has the disadvantage that the reaction process is long and the overall yield is low.
本発明は、簡便な方法で塩素イオンを含まない高純度のジアシル誘導体を得ることができる製造方法を提供することを目的とする。 An object of this invention is to provide the manufacturing method which can obtain the high purity diacyl derivative which does not contain a chlorine ion by a simple method.
本発明により、塩素イオンを含まない高純度のジアシル誘導体を極めて簡便な方法で、収率よく得ることができる。 According to the present invention, a high-purity diacyl derivative containing no chlorine ion can be obtained in a high yield by a very simple method.
本発明の方法によって製造されるジアシル誘導体は、ジアミンと重合することで、ポリアミド、ポリアミドイミド、ポリベンゾオキサゾール前駆体となり得るポリヒドロキシアミド、ポリベンゾイミダゾール前駆体となり得るポリアミノアミド、ポリベンゾチアゾール前駆体となり得るポリメルカプトアミドなどを製造することができる。得られたポリマーは塩素イオンを含まないため、半導体素子の保護膜、再配線膜、ディスプレーの絶縁膜など電気絶縁性が要求される用途に適用できる。 The diacyl derivative produced by the method of the present invention is polymerized with a diamine, so that polyamide, polyamideimide, polyhydroxyamide that can be a polybenzoxazole precursor, polyaminoamide that can be a polybenzimidazole precursor, polybenzothiazole precursor Polymercaptoamide or the like that can be produced can be produced. Since the obtained polymer does not contain chloride ions, it can be applied to applications requiring electrical insulation, such as a protective film for semiconductor elements, a rewiring film, and an insulating film for displays.
本発明は、一般式（１） The present invention relates to a general formula (1)
（式中、Ａは単結合、ＣＨ２、ＳＯ２、酸素原子、硫黄原子、Ｃ（ＣＨ３）２、または、Ｃ（ＣＦ３）２ を表し、Ｒ１、Ｒ２は、メチル基、エチル基、または、プロピル基を表し、ｍ、ｎおよびｐは０〜２の整数を表す。）
で表されるジカルボン酸と、一般式（２）
(In the formula, A represents a single bond, CH 2 , SO 2 , oxygen atom, sulfur atom, C (CH 3 ) 2 , or C (CF 3 ) 2 , and R 1 and R 2 represent a methyl group, ethyl Represents a group or a propyl group, and m, n and p represent an integer of 0 to 2.)
A dicarboxylic acid represented by the general formula (2)
で表される尿素誘導体を、含窒素有機溶媒の存在下で反応させて一般式（３） In represented by urea derivatives, is reacted in the presence of a nitrogen-containing organic solvent general formula (3)
（式中、Ａは、単結合、ＣＨ２、ＳＯ２、酸素原子、硫黄原子、Ｃ（ＣＨ３）２、または、Ｃ（ＣＦ３）２ を表し、Ｒ１、Ｒ２は、メチル基、エチル基、または、プロピル基を表し、ｍ、ｎおよびｐは０〜２の整数を表す。）
体の製造方法である。
(In the formula, A represents a single bond, CH 2 , SO 2 , oxygen atom, sulfur atom, C (CH 3 ) 2 , or C (CF 3 ) 2 , and R 1 and R 2 represent a methyl group, Represents an ethyl group or a propyl group, and m, n and p represent an integer of 0 to 2.)
It is a manufacturing method of a body.
本発明は、一般式（１） The present invention relates to a general formula (1)
（式中、Ａは単結合、ＣＨ２、ＳＯ２、酸素原子、硫黄原子、Ｃ（ＣＨ３）２、または、Ｃ（ＣＦ３）２ を表し、Ｒ１、Ｒ２は、メチル基、エチル基、または、プロピル基を表し、ｍ、ｎおよびｐは０〜２の整数を表す。）
で表されるジカルボン酸と、式（２）
(In the formula, A represents a single bond, CH 2 , SO 2 , oxygen atom, sulfur atom, C (CH 3 ) 2 , or C (CF 3 ) 2 , and R 1 and R 2 represent a methyl group, ethyl Represents a group or a propyl group, and m, n and p represent an integer of 0 to 2.)
A dicarboxylic acid represented by formula (2)
で表される尿素誘導体を、含窒素有機溶媒の存在下で反応させて一般式（３） In represented by urea derivatives, is reacted in the presence of a nitrogen-containing organic solvent general formula (3)
（式中、Ａは、単結合、ＣＨ２、ＳＯ２、酸素原子、硫黄原子、Ｃ（ＣＨ３）２、または、Ｃ（ＣＦ３）２ を表し、Ｒ１、Ｒ２は、メチル基、エチル基、または、プロピル基を表し、ｍ、ｎおよびｐは０〜２の整数を表す。）
で表されるジアシル誘導体を製造し、反応終了後、単離するジアシル誘導体の製造方法である。
(In the formula, A represents a single bond, CH 2 , SO 2 , oxygen atom, sulfur atom, C (CH 3 ) 2 , or C (CF 3 ) 2 , and R 1 and R 2 represent a methyl group, Represents an ethyl group or a propyl group, and m, n and p represent an integer of 0 to 2.)
Is a method for producing a diacyl derivative that is isolated after completion of the reaction.
一般式（１） General formula (1)
（式中、Ａは単結合、ＣＨ２、ＳＯ２、酸素原子、硫黄原子、Ｃ（ＣＨ３）２、または、Ｃ（ＣＦ３）２ を表し、Ｒ１、Ｒ２は、メチル基、エチル基、または、プロピル基を表し、ｍ、ｎおよびｐは０〜２の整数を表す。）
で表されるジカルボン酸において、Ａは、単結合、ＳＯ２または酸素原子がより好ましく、酸素原子がさらに好ましい。Ａが、単結合、ＳＯ２または酸素原子であると、ジアミンと重合して得られたポリマーを含む感光性樹脂組成物の露光感度が向上する。Ｒ１、Ｒ２は、メチル基、エチル基、プロピル基を表す。ｍ、ｎおよびｐは０〜２の整数を表し、０または１が好ましい。ｍが０、ｎが０、ｐが１であることがさらに好ましい。
(In the formula, A represents a single bond, CH 2 , SO 2 , oxygen atom, sulfur atom, C (CH 3 ) 2 , or C (CF 3 ) 2 , and R 1 and R 2 represent a methyl group, ethyl Represents a group or a propyl group, and m, n and p represent an integer of 0 to 2.)
In the dicarboxylic acid represented by A, A is preferably a single bond, SO 2 or an oxygen atom, and more preferably an oxygen atom. When A is a single bond, SO 2 or an oxygen atom, the exposure sensitivity of the photosensitive resin composition containing a polymer obtained by polymerization with diamine is improved. R 1, R 2 represents ethyl group, a propyl group. m , n and p represent an integer of 0 to 2, and 0 or 1 is preferable. More preferably, m is 0, n is 0, and p is 1 .
一般式（１）で表される具体的な化合物としては、好ましくは、下記構造のものを挙げることができる。 Specific examples of the compound represented by the general formula (1) preferably include the following structures.
一般式（１）で表される化合物は、より好ましくは、ビフェニルジカルボン酸、オキシ二安息香酸、スルホニル二安息香酸であり、オキシ二安息香酸がさらにより好ましい。 The compound represented by the general formula (1) is more preferably biphenyldicarboxylic acid, oxydibenzoic acid, or sulfonyldibenzoic acid, and even more preferably oxydibenzoic acid.
式（２）で表される化合物は、１，１’−カルボニルジイミダゾールである。 Ru of Gobutsu represented by formula (2) is 1, a 1'-carbonyldiimidazole imidazole.
式（２）で表される化合物は一般式（１）で表される化合物に対して、２．０〜５．０モル倍用いることが好ましく、２．１〜３．０モル倍用いることがより好ましい。 The compound represented by the formula (2) is preferably used in an amount of 2.0 to 5.0 moles, more preferably 2.1 to 3.0 moles, relative to the compound represented by the general formula (1). More preferred.
本発明の製造方法において、一般式（１）で表される化合物と式（２）で表される化合物を反応させるために含窒素有機溶媒を用いる。含窒素有機溶媒は、Ｎ−メチルー２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミドが好ましい。含窒素有機溶媒は、単独で使用してもよく、複数種組み合わせて用いてもよい。 In the production method of the present invention, a nitrogen-containing organic solvent is used for reacting the compound represented by the general formula (1) with the compound represented by the formula (2) . Nitrogen-containing organic solvents, N - methyl-2-pyrrolidone, N, N- dimethylacetamide, N, N-dimethylformamide is good preferable. A nitrogen-containing organic solvent may be used independently and may be used in combination of multiple types.
有機溶媒の使用量は一般式（１）の化合物に対して１から４０重量倍用いるのが好ましく、２から２０重量倍用いるのがより好ましい。 The amount of the organic solvent used is preferably 1 to 40 times by weight, more preferably 2 to 20 times by weight based on the compound of the general formula (1).
本発明のジアシル誘導体の製造方法において、反応温度は０℃〜溶媒の沸点の範囲が好適であるが、室温から１００℃の範囲がより好ましい。反応時間は１時間から１週間が好ましく、２時間から１日がより好ましい。反応の雰囲気としては、窒素、アルゴン等の不活性ガス雰囲気が好ましい。 In the method for producing a diacyl derivative of the present invention, the reaction temperature is preferably in the range of 0 ° C. to the boiling point of the solvent, more preferably in the range of room temperature to 100 ° C. The reaction time is preferably 1 hour to 1 week, more preferably 2 hours to 1 day. As the reaction atmosphere, an inert gas atmosphere such as nitrogen or argon is preferable.
本発明の方法によって製造される一般式（３）で表される具体的な化合物としては、例えば、下記構造のものを挙げることができる。 Specific examples of the compound represented by the general formula (3) produced by the method of the present invention include those having the following structures.
本発明のジアシル誘導体の製造方法は、一般式（３）で表される化合物が、１，１’−（オキシジベンゾイル）ジイミダゾール、または、１，１’−（ジベンゾイル）ジイミダゾールである場合に特に有効である。 If it is (dibenzoyl) Jiimidazo Le - method of manufacturing diacyl derivatives of the present invention is a compound represented by the general formula (3) is 1,1 '- (oxy dibenzoyl) diimidazole or 1,1' Is particularly effective.
本発明のジアシル誘導体の製造方法では、反応終了後、目的の化合物は、抽出、濃縮、晶析、ろ過、カラムクロマトグラフィーなどの方法で単離する。目的物の沈殿が発生しているものはろ過を行い、目的のジアシル誘導体を得ることができる。 In the method for producing a diacyl derivative of the present invention, after completion of the reaction, the target compound is isolated by a method such as extraction, concentration, crystallization, filtration, or column chromatography . Those in which precipitation of the target product has occurred can be filtered to obtain the target diacyl derivative.
本発明のジアシル誘導体の製造方法では、反応終了後、水やアルコール類、ケトン類から選ばれる少なくとも１種類の溶媒を添加して、ろ過を行うか、または、常圧、もしくは減圧下で濃縮して溶媒を一部留去した後、から選ばれる少なくとも１種類の溶媒を添加して、ろ過を行い、目的のジアシル誘導体を得ることもできる。 In the method for producing a diacyl derivative of the present invention, after the reaction is completed, at least one solvent selected from water, alcohols, and ketones is added, followed by filtration, or concentration under normal pressure or reduced pressure. Then, after partially distilling off the solvent, at least one solvent selected from the following can be added and filtered to obtain the desired diacyl derivative.
本発明のジアシル誘導体の製造方法では、目的物の沈殿から、ナトリウム、鉄などの金属を低減させるために、水やアルコール類、ケトン類から選ばれる少なくとも１種類の溶媒で洗浄を行うことが好ましい。水、アルコール類、ケトン類から選ばれる少なくとも１種類の溶媒の使用量は、一般式（１）の化合物に対して０．１から２０重量倍用いるのが好ましく、１から１０重量倍用いるのがより好ましい。アルコール類としては、イソプロパノール、イソブタノールなどが好ましく、ケトン類としては、アセトン、メチルエチルケトンなどが好ましい。反応終了後に添加、洗浄に用いる水、アルコール類、ケトン類から選ばれる少なくとも１種類の溶媒は、単独、または複数組み合わせて用いても良い。 In the method for producing a diacyl derivative of the present invention, it is preferable to perform washing with at least one solvent selected from water, alcohols and ketones in order to reduce metals such as sodium and iron from precipitation of the target product. . The amount of at least one solvent selected from water, alcohols and ketones is preferably 0.1 to 20 times by weight, preferably 1 to 10 times by weight, relative to the compound of the general formula (1). More preferred. As alcohols, isopropanol, isobutanol and the like are preferable, and as ketones, acetone, methyl ethyl ketone and the like are preferable. At least one solvent selected from water, alcohols and ketones used for addition and washing after completion of the reaction may be used alone or in combination.
また、必要により、本発明のジアシル誘導体の製造方法で製造されたジアシル誘導体は、再結晶、再沈、カラムクロマトグラフィーなどの方法により精製することもできる。再結晶する場合は、目的物と反応することがない溶媒を、単独もしくは複数種組み合わせて行うことができる。 Moreover, the diacyl derivative manufactured by the manufacturing method of the diacyl derivative of this invention can also be refine | purified by methods, such as recrystallization, reprecipitation, and column chromatography, as needed. In the case of recrystallization, solvents that do not react with the target product can be used alone or in combination of two or more.
このようにして得られたジアシル誘導体は、水分、溶媒分を除去して乾燥することが好ましい。 The diacyl derivative thus obtained is preferably dried after removing moisture and solvent.
以下に、実施例に基づいて本発明をより詳細に説明する。 Below, based on an Example, this invention is demonstrated in detail.
実施例１
１，１’−（４，４’−オキシジベンゾイル）ジイミダゾール
Example 1
1,1 ′-(4,4′-oxydibenzoyl) diimidazole
温度計、三方コック、攪拌機を備えた１Ｌの４つ口フラスコに窒素気流下、１，１’−カルボニルジイミダゾール（東京化成工業（株）社製）１０６．６ｇ（０．６６モル）とＮ−メチル−２−ピロリドン(ＮＭＰ)（ナカライテスク社製）５５７ｇを仕込んだ。室温で攪拌して溶解した後、４，４’−オキシ二安息香酸（東京化成工業（株）社製、Ｆｅは１０ｐｐｍ、Ｎａは１２ｐｐｍであった）７５．５ｇ（０．２９モル）を３６℃以下で添加し、攪拌した。６２℃まで昇温し、炭酸ガスの発生が終了後、５℃以下まで冷却し、イオン交換水４１５．６ｇを１０℃以下で滴下し、沈殿を濾過した。沈殿をイオン交換水６８．５ｇ、イソプロパノール（ナカライテスク社製）１５３．４ｇで洗浄後、５０℃で減圧乾燥し、１，１’−（４，４’−オキシジベンゾイル）ジイミダゾールを１０３．６ｇ（収率：９９％）得た。ＨＰＬＣ純度は９９％であった。Ｆｅ及びＮａの含有量を誘導結合プラズマ質量分析装置(ＩＣＰ−ＭＳ）により分析した結果、Ｆｅ、Ｎａともに１ｐｐｍ以下であった。 In a 1 L four-necked flask equipped with a thermometer, a three-way cock, and a stirrer, 106.6 g (0.66 mol) and 1,1′-carbonyldiimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) under nitrogen flow. -557 g of methyl-2-pyrrolidone (NMP) (manufactured by Nacalai Tesque) was charged. After stirring and dissolving at room temperature, 75.5 g (0.29 mol) of 4,4′-oxydibenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd., Fe was 10 ppm, Na was 12 ppm) was obtained. The mixture was added at a temperature not higher than ° C. and stirred. The temperature was raised to 62 ° C., and after the generation of carbon dioxide gas was completed, the temperature was lowered to 5 ° C. or lower, 415.6 g of ion-exchanged water was dropped at 10 ° C. or lower, and the precipitate was filtered. The precipitate was washed with 68.5 g of ion-exchanged water and 153.4 g of isopropanol (manufactured by Nacalai Tesque), and then dried under reduced pressure at 50 ° C. to obtain 103. 1,1 ′-(4,4′-oxydibenzoyl) diimidazole. 6 g (yield: 99%) was obtained. The HPLC purity was 99%. As a result of analyzing the content of Fe and Na by an inductively coupled plasma mass spectrometer (ICP-MS), both Fe and Na were 1 ppm or less.
ＩＲ（ＡＴＲ）ｃｍ−１：１６９４、１５８９、１２５１；１ＨＮＭＲ δ ｐｐｍ（ＣＤＣｌ３，４００ＭＨｚ）：７．２０（ｓ，２Ｈ）、７．２５（ｄ，４Ｈ，Ｊ＝８．３Ｈｚ）、７．５６（Ｓ，２Ｈ）、７．９０（ｄ，４Ｈ，Ｊ＝８．３Ｈｚ）、８．１１（ｓ，２Ｈ）。 IR (ATR) cm −1 : 1694, 1589, 1251; 1 HNMR δ ppm (CDCl 3 , 400 MHz): 7.20 (s, 2H), 7.25 (d, 4H, J = 8.3 Hz), 7 .56 (S, 2H), 7.90 (d, 4H, J = 8.3 Hz), 8.11 (s, 2H).
実施例２
１，１’−（４，４’−オキシジベンゾイル）ジイミダゾール
温度計、三方コック、滴下ロート、攪拌機を備えた１Ｌの４つ口フラスコに窒素気流下、１，１’−カルボニルジイミダゾール（東京化成工業（株）社製）３５．１７ｇ（０．２１７モル）とＮ，Ｎ−ジメチルホルムアミド(ＤＭＦ) （ナカライテスク社製）１７８ｇを仕込んだ。４，４’−オキシ二安息香酸（東京化成工業（株）社製）２５．０４ｇ（０．０９７モル）をＤＭＦ１３１ｇに溶解した溶液を滴下ロートから１５分間で滴下した。６７−６９℃（３０−３６Ｔｏｒｒ）で溶媒を濃縮し、留出液が１９５ｇになった時点で濃縮を終了し、窒素気流下、１０℃以下まで冷却し、アセトン（ナカライテスク社製）１９５ｇを滴下し、沈殿をろ過した。沈殿をイソプロパノール（ナカライテスク社製）５０ｇで洗浄後、６５℃で減圧乾燥し、１，１’−（４，４’−オキシジベンゾイル）ジイミダゾールを３０．８６ｇ（収率：９５％）得た。ＨＰＬＣ純度は９９％であった。Ｆｅ及びＮａの含有量を分析した結果、Ｆｅ、Ｎａ共に１ｐｐｍ以下であった。
Example 2
1,1 ′-(4,4′-oxydibenzoyl) diimidazole thermometer, three-way cock, dropping funnel, 1 L four-necked flask equipped with a stirrer was subjected to 1,1′-carbonyldiimidazole ( Tokyo Chemical Industry Co., Ltd.) 35.17 g (0.217 mol) and N, N-dimethylformamide (DMF) (Nacalai Tesque) 178 g were charged. A solution prepared by dissolving 25.04 g (0.097 mol) of 4,4′-oxydibenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) in 131 g of DMF was dropped from a dropping funnel over 15 minutes. The solvent was concentrated at 67-69 ° C. (30-36 Torr). When the distillate reached 195 g, the concentration was completed. The mixture was cooled to 10 ° C. or lower under a nitrogen stream, and 195 g of acetone (manufactured by Nacalai Tesque) was added. The solution was added dropwise and the precipitate was filtered. The precipitate was washed with 50 g of isopropanol (Nacalai Tesque) and then dried under reduced pressure at 65 ° C. to obtain 30.86 g (yield: 95%) of 1,1 ′-(4,4′-oxydibenzoyl) diimidazole. It was. The HPLC purity was 99%. As a result of analyzing the contents of Fe and Na, both Fe and Na were 1 ppm or less.
実施例３
テレフタロイルジイミダゾール
Example 3
Terephthaloyldiimidazole
温度計、三方コック、攪拌機を備えた１００ｍＬの３つ口フラスコに窒素気流下、テレフタル酸（東京化成工業（株）社製）３．３８ｇ（０．０２０モル）とＮＭＰ（ナカライテスク社製）２２ｇを仕込んで攪拌した。１，１’−カルボニルジイミダゾール（東京化成工業（株）社製）７．３２ｇ（０．０４５モル）を数回にわけて添加した。室温で１．５時間攪拌後、アセトン（ナカライテスク社製）１１．９ｇを滴下し、生じた沈殿を濾過した。沈殿をアセトン７ｇで洗浄後、５０℃で減圧乾燥し、テレフタロイルジイミダゾールを５．１４ｇ（収率：９５％）得た。ＨＰＬＣ純度は９７％であった。 Under a nitrogen stream, 3.38 g (0.020 mol) of terephthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and NMP (manufactured by Nacalai Tesque) in a 100 mL three-necked flask equipped with a thermometer, a three-way cock, and a stirrer 22 g was charged and stirred. 7.32 g (0.045 mol) of 1,1'-carbonyldiimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in several portions. After stirring at room temperature for 1.5 hours, 11.9 g of acetone (manufactured by Nacalai Tesque) was added dropwise, and the resulting precipitate was filtered. The precipitate was washed with 7 g of acetone and then dried under reduced pressure at 50 ° C. to obtain 5.14 g (yield: 95%) of terephthaloyldiimidazole. The HPLC purity was 97%.
ＩＲ（ＡＴＲ）ｃｍ−１：１７０９、１２４８；１ＨＮＭＲ δ ｐｐｍ（ＤＭＳＯ−ｄ６、４００ＭＨｚ）：７．１９（ｔ，２Ｈ，Ｊ＝１．２Ｈｚ）、７．７５（ｔ，２Ｈ，Ｊ＝１．２Ｈｚ）、８．００（ｄ．４Ｈ．Ｊ＝０．４Ｈｚ）、８．２７（ｄ，２Ｈ，Ｊ＝０．８Ｈｚ） 。 IR (ATR) cm −1 : 1709, 1248; 1 HNMR δ ppm (DMSO-d 6 , 400 MHz): 7.19 (t, 2H, J = 1.2 Hz), 7.75 (t, 2H, J = 1.2 Hz), 8.00 (d.4H.J = 0.4 Hz), 8.27 (d, 2H, J = 0.8 Hz).
実施例４
１，１’−（４，４’−ジベンゾイル）ジイミダゾール
Example 4
1,1 ′-(4,4′-dibenzoyl) diimidazole
実施例２において、４，４’−オキシ二安息香酸のかわりに、４，４’−ビフェニルジカルボン酸（東京化成工業（株）社製）を用いる以外は実施例２と同様の操作をして、１，１’−（４，４’−ジベンゾイル）ジイミダゾールを得た。収率は９５％、ＨＰＬＣ純度は９７％であった。 In Example 2, the same operation as in Example 2 was performed except that 4,4′-biphenyldicarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 4,4′-oxydibenzoic acid. 1,1 ′-(4,4′-dibenzoyl) diimidazole was obtained. The yield was 95% and the HPLC purity was 97%.
参考例１
１，１‘−（４，４’−オキシジベンゾイル）ビス（２−メチルイミダゾール）
Reference example 1
1,1 ′-(4,4′-oxydibenzoyl) bis (2-methylimidazole)
実施例２において、１，１’−カルボニルジイミダゾールのかわりに、１，１’−カルボニルビス（２−メチルイミダゾール）（Ａｌｄｒｉｃｈ社製）を用いる以外は実施例２と同様の操作をして、１，１‘−（４，４’−オキシジベンゾイル）ビス（２−メチルイミダゾール）を得た。収率は９５％、ＨＰＬＣ純度は９７％であった。 In Example 2, instead of 1,1′-carbonyldiimidazole, the same operation as in Example 2 was performed except that 1,1′-carbonylbis (2-methylimidazole) (manufactured by Aldrich) was used. 1,1 ′-(4,4′-oxydibenzoyl) bis (2-methylimidazole) was obtained. The yield was 95% and the HPLC purity was 97%.
比較例１
１，１’−（４，４’−オキシジベンゾイル）ジイミダゾール
温度計、三方コック、攪拌機、滴下ロートを備えた５００ｍＬの３つ口フラスコに窒素気流下、４，４’−オキシ二安息香酸（東京化成工業（株）社製）２３．５０ｇ（０．０９１モル）、ＴＨＦ（ナカライテスク社製）２００ｇを加え、室温で攪拌しながら、ＤＭＦ（ナカライテスク社製）６滴を添加し、滴下ロートから塩化チオニル（ナカライテスク社製）２３．８ｇ（０．２０モルを滴下した後、４時間加熱還流した。加熱してＴＨＦ１１０ｇを留去した後、冷却し、トルエン（ナカライテスク社製）３７ｇを加えて攪拌し、不溶物をろ過した。ろ液を濃縮乾固して４２．７ｇの４，４’−オキシジベンゾイルクロリドの粗体を得た。ここにＴＨＦ１２５ｇを加え溶解しＴＨＦ溶液を調製した。
Comparative Example 1
1,4'-oxydibenzoic acid in a 500 mL three-necked flask equipped with a 1,1 '-(4,4'-oxydibenzoyl) diimidazole thermometer, three-way cock, stirrer, and dropping funnel under a nitrogen stream 23.50 g (0.091 mol) (manufactured by Tokyo Chemical Industry Co., Ltd.), 200 g of THF (manufactured by Nacalai Tesque) are added, and 6 drops of DMF (manufactured by Nacalai Tesque) are added while stirring at room temperature. From the dropping funnel, 23.8 g of thionyl chloride (manufactured by Nacalai Tesque) (0.20 mol was added dropwise and then heated to reflux for 4 hours. After heating to distill off 110 g of THF, the mixture was cooled and toluene (manufactured by Nacalai Tesque) 37 g was added and stirred, and insoluble matter was filtered off, and the filtrate was concentrated to dryness to obtain 42.7 g of a crude product of 4,4′-oxydibenzoyl chloride, which was dissolved in 125 g of THF and dissolved in THF. A liquid was prepared.
温度計、三方コック、攪拌機、滴下ロートを備えた５００ｍＬの３つ口フラスコに窒素気流下、イミダゾール（東京化成工業（株）社製）２４．９３ｇ（０．３６６モル）、ＴＨＦ９０ｇを加え室温で攪拌し、先ほど調製した、４，４’−オキシジベンゾイルクロリドのＴＨＦ溶液を滴下ロートから３０分間で滴下し、３時間室温で攪拌した後、沈殿をろ過し、得られた沈殿をビーカーに入れ、イオン交換水９５ｇ、イソプロパノール１０２ｇを加えて室温で１．５時間攪拌した後、ろ過し、沈殿をイソプロパノール１１２ｇで洗浄し、５０℃で減圧乾燥し、１，１’−（４，４’−オキシジベンゾイル）ジイミダゾールを２１．６ｇ（収率：６６％）得た。ＨＰＬＣ純度は、８６％であった。 Under a nitrogen stream, 24.93 g (0.366 mol) of imidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) and 90 g of THF were added to a 500 mL three-necked flask equipped with a thermometer, a three-way cock, a stirrer, and a dropping funnel at room temperature. Stir the 4,4′-oxydibenzoyl chloride THF solution prepared above in 30 minutes from the dropping funnel, stir for 3 hours at room temperature, filter the precipitate, and place the resulting precipitate in a beaker. Then, 95 g of ion-exchanged water and 102 g of isopropanol were added and stirred at room temperature for 1.5 hours, followed by filtration. The precipitate was washed with 112 g of isopropanol, dried under reduced pressure at 50 ° C., and 1,1 ′-(4,4′- 21.6 g (yield: 66%) of oxydibenzoyl) diimidazole was obtained. The HPLC purity was 86%.
Claims (4)
で表されるジカルボン酸と、式（２）
で表されるジアシル誘導体を製造し、反応終了後、単離するジアシル誘導体の製造方法。 General formula (1)
A dicarboxylic acid represented by formula (2)
The manufacturing method of the diacyl derivative which manufactures the diacyl derivative represented by these, and isolates after completion | finish of reaction.
で表されるジカルボン酸と、式（２）
で表されるジアシル誘導体を製造し、反応終了後、単離して、水、アルコール類、ケトン類から選ばれる少なくとも１種類の溶媒で洗浄するジアシル誘導体の製造方法。 General formula (1)
A dicarboxylic acid represented by formula (2)
A diacyl derivative represented by the following formula is prepared, and after completion of the reaction, the diacyl derivative is isolated and washed with at least one solvent selected from water, alcohols and ketones.
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