JP6088890B2 - Acyltriazole derivative and process for producing the same - Google Patents
Acyltriazole derivative and process for producing the same Download PDFInfo
- Publication number
- JP6088890B2 JP6088890B2 JP2013076101A JP2013076101A JP6088890B2 JP 6088890 B2 JP6088890 B2 JP 6088890B2 JP 2013076101 A JP2013076101 A JP 2013076101A JP 2013076101 A JP2013076101 A JP 2013076101A JP 6088890 B2 JP6088890 B2 JP 6088890B2
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- JP
- Japan
- Prior art keywords
- group
- acyltriazole
- derivative
- triazole
- carboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title description 12
- -1 naphthalenediyl group Chemical group 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 14
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
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- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 22
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 20
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- 238000006243 chemical reaction Methods 0.000 description 15
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- QQVDYSUDFZZPSU-UHFFFAOYSA-M chloromethylidene(dimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)=CCl QQVDYSUDFZZPSU-UHFFFAOYSA-M 0.000 description 9
- 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 8
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- 125000001424 substituent group Chemical group 0.000 description 8
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- 229910052801 chlorine Inorganic materials 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
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- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 4
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- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 3
- GDYYIJNDPMFMTB-UHFFFAOYSA-N 2-[3-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC(CC(O)=O)=C1 GDYYIJNDPMFMTB-UHFFFAOYSA-N 0.000 description 3
- UETNUHBZKZHKCL-UHFFFAOYSA-N 2-[4-(2-chloro-2-oxoethyl)phenyl]acetyl chloride Chemical compound ClC(=O)CC1=CC=C(CC(Cl)=O)C=C1 UETNUHBZKZHKCL-UHFFFAOYSA-N 0.000 description 3
- HXTYZWJVMWWWDK-IZLXSQMJSA-N ClC(=O)[C@H]1CC[C@@H](CC1)C(Cl)=O Chemical compound ClC(=O)[C@H]1CC[C@@H](CC1)C(Cl)=O HXTYZWJVMWWWDK-IZLXSQMJSA-N 0.000 description 3
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- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 3
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 2
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 description 2
- SLWIPPZWFZGHEU-UHFFFAOYSA-N 2-[4-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=C(CC(O)=O)C=C1 SLWIPPZWFZGHEU-UHFFFAOYSA-N 0.000 description 2
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical class OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-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
- 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 2
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- FAINTUWDSUENCH-ZKCHVHJHSA-N O=C([C@H](CC1)CC[C@@H]1C(C1=CNN=N1)=O)C1=CNN=N1 Chemical compound O=C([C@H](CC1)CC[C@@H]1C(C1=CNN=N1)=O)C1=CNN=N1 FAINTUWDSUENCH-ZKCHVHJHSA-N 0.000 description 2
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- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
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- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 2
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- 231100000419 toxicity Toxicity 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Polyamides (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
本発明は、新規なアシルトリアゾール誘導体およびその製造方法に関する。 The present invention relates to a novel acyltriazole derivative and a method for producing the same.
芳香族ポリアミドおよび芳香族ポリエステルは高い耐熱性を有し、この性質を利用して様々な用途への展開が進められている。これらのポリマーは、芳香族ジカルボン酸とジアミン、ジアルコール、ビスフェノール類との縮合反応により合成することが一般的である。しかし、芳香族ジカルボン酸は溶媒への溶解性に乏しく、反応性において問題となる場合がしばしばある。その改善方法として芳香族ジカルボン酸クロリドを用いる方法が知られている。
一方、ポリマーの柔軟性および光透過性を考慮するときには、脂肪族のポリアミドおよびポリエステルが適しており、これも研究の対象として様々な分野で注目されている。その原料としても、脂肪族ジカルボン酸クロリドは有用であり広く利用されている。
Aromatic polyamides and aromatic polyesters have high heat resistance, and are being developed for various applications using this property. These polymers are generally synthesized by a condensation reaction between an aromatic dicarboxylic acid and a diamine, dialcohol, or bisphenol. However, aromatic dicarboxylic acids have poor solubility in solvents and often become a problem in reactivity. As an improvement method, a method using an aromatic dicarboxylic acid chloride is known.
On the other hand, when considering the flexibility and light transmittance of the polymer, aliphatic polyamides and polyesters are suitable, and these are also attracting attention in various fields as research objects. As the raw material, aliphatic dicarboxylic acid chloride is useful and widely used.
ところで、マイクロエレクトロニクス分野においては、微量の金属イオン、ハロゲン化物イオンが電気的機能に悪影響を及ぼす場合がある。そこで、そのような用途においては、合成原料としてハロゲンを含むものを避け、ジカルボン酸エステル、特に活性エステルがしばしば使用される。その一例として、ヒドロキシベンゾトリアゾールのエステル体やイミダゾール誘導体が提案されている（特許文献１，４、非特許文献１参照）。 Incidentally, in the microelectronics field, a trace amount of metal ions and halide ions may adversely affect the electrical function. Therefore, in such applications, dicarboxylic acid esters, particularly active esters are often used, avoiding those containing halogen as a synthetic raw material. For example, hydroxybenzotriazole esters and imidazole derivatives have been proposed (see Patent Documents 1 and 4 and Non-Patent Document 1).
上述したカルボン酸を有する化合物と１−ヒドロキシベンゾトリアゾールとのエステル体を合成するには、当量以上のエステル縮合剤が必要となる。これに代え、カルボン酸ジクロリドと１−ヒドロキシベンゾトリアゾールとを反応させる方法が考えられるが、そのためには１−ヒドロキシベンゾトリアゾールを無水物としなければならない。しかし、結晶水を含まないヒドロキシベンゾトリアゾールは爆発性があり、工業的使用においてその方法を採用するには難がある。
活性エステルとしてベンゾチアゾール、ベンゾイミダゾールを用いる方法が提案されているが（特許文献２，３）、合成方法が複雑である。カルボン酸ジクロリドをアシルイミダゾール誘導体とする方法も提案されている（特許文献４）。この方法によればアシルイミダゾール誘導体の合成は可能である。しかし、芳香族カルボン酸のアシルイミダゾール誘導体は、アミンまたはアルコール・フェノールなどとの反応性が芳香族カルボン酸ジクロリドに比べて極端に低く、エステルまたはアミドを合成するのに長時間を要する（後記比較例参照）。最近、活性エステルとしてトリアジン誘導体が提案されたが、その合成方法も特殊な縮合反応を必要とする（特許文献５）。
In order to synthesize the ester of the above-described compound having a carboxylic acid and 1-hydroxybenzotriazole, an ester condensing agent of an equivalent amount or more is required. Instead of this, a method of reacting carboxylic acid dichloride with 1-hydroxybenzotriazole is conceivable. For this purpose, 1-hydroxybenzotriazole must be converted into an anhydride. However, hydroxybenzotriazole containing no crystallization water is explosive and it is difficult to adopt the method for industrial use.
Although methods using benzothiazole or benzimidazole as active esters have been proposed (Patent Documents 2 and 3), the synthesis method is complicated. A method in which carboxylic acid dichloride is an acylimidazole derivative has also been proposed (Patent Document 4). According to this method, an acylimidazole derivative can be synthesized. However, acyl imidazole derivatives of aromatic carboxylic acids are extremely less reactive with amines, alcohols, phenols, etc. than aromatic carboxylic acid dichlorides, and it takes a long time to synthesize esters or amides (see below for comparison). See example). Recently, triazine derivatives have been proposed as active esters, but the synthesis method also requires a special condensation reaction (Patent Document 5).
上述の従来技術の状況に鑑み、本発明は、安価かつ簡便な方法で合成することができ、アミン化合物やアルコール化合物に対して酸クロリドに匹敵する反応性を有し、しかも安全に取り扱うことができる新規アシルトリアゾール誘導体およびその製造方法の提供を目的とする。また、引き続く重合反応に適用する反応基質として有用なアシルトリアゾール誘導体およびこれからなるモノマーの提供を目的とする。 In view of the above-described state of the prior art, the present invention can be synthesized by an inexpensive and simple method, has reactivity comparable to acid chloride with respect to amine compounds and alcohol compounds, and can be handled safely. It is an object to provide a novel acyltriazole derivative that can be produced and a method for producing the same. Another object of the present invention is to provide an acyltriazole derivative useful as a reaction substrate applied to the subsequent polymerization reaction and a monomer comprising the acyltriazole derivative.
本発明者は、上記の課題に対して鋭意研究開発を進めた結果、前記カルボン酸のエステル体を合成するに当たり１，３−イミダゾールの代わりに１，２，４−トリアゾールを用いることで、上記の要求項目を満足することができることを見出した。すなわち、上記の技術課題は下記の手段により解決された。 As a result of diligent research and development on the above problems, the present inventor used 1,2,4-triazole instead of 1,3-imidazole to synthesize the ester of the carboxylic acid. It was found that the required items can be satisfied. That is, the above technical problem has been solved by the following means.
〔１〕下記式（１）、（１Ａ）、（１Ｂ）、（１Ｃ）または（１Ｄ）で表されるアシルトリアゾール誘導体。
〔２〕ジアミン化合物もしくはジオール化合物と反応させ、ポリアミドもしくはポリエステルを得るためのモノマーとして使用する、〔１〕に記載のアシルトリアゾール誘導体。
[1] An acyltriazole derivative represented by the following formula (1) , (1A), (1B), (1C) or (1D) .
[2] is reacted with di-amine compound or diol compound, be used as a monomer for obtaining a polyamide or polyester, acyl triazole induction body according to [1].
本発明の新規アシルトリアゾール誘導体は、ハロゲンを含まず環境適合性に優れ、安価かつ容易に合成することができる。そのポリマー合成における反応性はカルボン酸クロリドに匹敵するものであり、ハロゲンフリーのポリアミド・ポリエステル等を合成する反応基質として極めて有用である。また、必要により、前記ポリマー合成に適用するに際し、前記アシルトリアゾール誘導体の前駆体であるカルボン酸クロリド類として低融点ないし溶媒溶解性の良好なものを選定することもできる。さらに、本発明の製造方法によれば、上記の有用な新規アシルトリアゾール誘導体を高い生産効率で、安価かつ簡便に製造することができる。 The novel acyltriazole derivative of the present invention does not contain halogen, is excellent in environmental compatibility, and can be synthesized inexpensively and easily. The reactivity in polymer synthesis is comparable to that of carboxylic acid chloride, and it is extremely useful as a reaction substrate for synthesizing halogen-free polyamides and polyesters. If necessary, when applying to the polymer synthesis, carboxylic acid chlorides which are precursors of the acyltriazole derivatives can be selected from those having a low melting point or good solvent solubility. Furthermore, according to the production method of the present invention, the useful novel acyltriazole derivative can be produced with high production efficiency at low cost and in a simple manner.
以下、本発明についてその好ましい実施態様に基づき詳細に説明する。
［新規アシルトリアゾール誘導体］
本発明の新規アシルトリアゾール誘導体は下記式（１）で表される構造を有する。
Hereinafter, the present invention will be described in detail based on preferred embodiments thereof.
[New acyltriazole derivatives]
The novel acyltriazole derivative of the present invention has a structure represented by the following formula (1).
式（１）中、Ａは置換アリーレン基、１，３−フェニレン基、ビスアリーレン基、多環アリーレン基、またはアルキレン基を表す。なかでも、炭素数６〜８の置換アリーレン基、炭素数６〜８の置換または無置換の１，３−フェニレン基、炭素数１２〜１６のビスアリーレン基、炭素数１２〜１６のアリーレン基、炭素数４〜１０のアルキレン基、炭素数８〜１２のアラルキレン基が好ましい。 In formula (1), A represents a substituted arylene group, a 1,3-phenylene group, a bisarylene group, a polycyclic arylene group, or an alkylene group. Among them, a substituted arylene group having 6 to 8 carbon atoms, a substituted or unsubstituted 1,3-phenylene group having 6 to 8 carbon atoms, a bisarylene group having 12 to 16 carbon atoms, an arylene group having 12 to 16 carbon atoms, An alkylene group having 4 to 10 carbon atoms and an aralkylene group having 8 to 12 carbon atoms are preferable.
・アリーレン基
置換アリーレン基としては、アルキル置換フェニレン基が好ましく、下記式（Ａ１）の連結基がより好ましい。
１，３−フェニレン基は置換基を有していてもよく、当該任意の置換基としては、前記置換基Ｒが挙げられる。 The 1,3-phenylene group may have a substituent, and examples of the optional substituent include the substituent R.
本発明のアシルトリアゾール誘導体には、式（１）においてＡが無置換の１，４−フェニレン基のものは含まれない。 The acyltriazole derivative of the present invention does not include those in which A is an unsubstituted 1,4-phenylene group in the formula (1).
・ビスアリーレン基
ビスアリーレン基とは、単結合もしくは所定の連結基を介してアリーレン基が２つ結合された構造を有する連結基を意味する。本発明において、ビスアリーレン基は下記式（Ｉ）で表される連結基であることが好ましい。
-Bisarylene group A bisarylene group means a linking group having a structure in which two arylene groups are bonded via a single bond or a predetermined linking group. In the present invention, the bisarylene group is preferably a linking group represented by the following formula (I).
Ｒ１、Ｒ２は置換基を表す。その好ましいものは、アルキル基（好ましくは炭素原子数１〜４のアルキル基、例えばメチル、エチル、イソプロピル、ｔ−ブチル等）、アルコキシ基（好ましくは炭素原子数１〜４のアルコキシ基、例えば、メトキシ、エトキシ、イソプロピルオキシ等）、フッ素原子または塩素原子などが挙げられる。 R 1 and R 2 represent a substituent. Preferred are alkyl groups (preferably alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, isopropyl, t-butyl etc.), alkoxy groups (preferably alkoxy groups having 1 to 4 carbon atoms such as Methoxy, ethoxy, isopropyloxy, etc.), fluorine atom or chlorine atom.
ｎ１、ｎ２は０〜４の整数を表し、０〜２の整数が好ましく、０〜１がより好ましい。 n1 and n2 represent an integer of 0 to 4, an integer of 0 to 2 is preferable, and 0 to 1 is more preferable.
Ｌ１、Ｌ２は単結合もしくは連結基を表す。連結基の好ましい範囲としては、環状もしくは鎖状のアルキレン基、アリーレン基、ヘテロ環基、オキシ基（−Ｏ−）、カルボニル基、アミノ基（−ＮＲ−：Ｒは水素原子もしくは有機基）、またはそれらの組合せが挙げられる。Ｌ１、Ｌ２は中でも、単結合もしくは炭素数１〜６のアルキレン基が好ましく、単結合がより好ましい。 L 1 and L 2 represent a single bond or a linking group. Preferred examples of the linking group include a cyclic or chain alkylene group, an arylene group, a heterocyclic group, an oxy group (—O—), a carbonyl group, an amino group (—NR—: R is a hydrogen atom or an organic group), Or a combination thereof. Among these, L 1 and L 2 are preferably a single bond or an alkylene group having 1 to 6 carbon atoms, and more preferably a single bond.
Ａ１は単結合または連結基を表す。その連結基の例としては、−Ｏ−、−ＣＨ２−、−Ｃ（ＣＨ３）Ｈ−、−Ｃ（ＣＨ３）２−、−Ｃ（ＣＨ３）（Ｐｈ）−、−Ｃ（ＣＦ３）２−、−Ｃ（ＣＨ３）（Ｃ２Ｈ５）−、−Ｃ（Ｐｈ）２−、Ｃ（＝ＣＣｌ２）−、−Ｃ（ＣＨ３）Ｈ−、−ＳＯ２−などが挙げられる。ここで、「Ｐｈ」はフェニル基の意味である。 A 1 represents a single bond or a linking group. Examples of the linking group include —O—, —CH 2 —, —C (CH 3 ) H—, —C (CH 3 ) 2 —, —C (CH 3 ) (Ph) —, —C (CF 3) 2 -, - C ( CH 3) (C 2 H 5) -, - C (Ph) 2 -, C (= CCl 2) -, - C (CH 3) H -, - SO 2 - and Can be mentioned. Here, “Ph” means a phenyl group.
Ａ１として、下記式で表されるものも挙げられる。 Examples of A 1 include those represented by the following formula.
連結基Ａがビスアリーレン基であるとき、これがビフェニルエーテル連結基においてその４，４’位で連結された下記式（１Ａ）の化合物であることが好ましい。 When the linking group A is a bisarylene group, it is preferably a compound of the following formula (1A) linked at the 4,4′-position in the biphenyl ether linking group.
・多環アリーレン基
連結基Ａが多環アリーレン基であるとき、その縮合した環の数は２〜４であることが好ましい。具体的には、ナフタレンジイル基、アントラセンジイル基、フェナントレンジイル基、トリフェニレンジイル基などが好ましく、ナフタレンジイル基がより好ましい。このとき、上記で例示した多環芳香族連結基は、さらに置換基を有していてもよく、その置換基としては前記Ｒ１の例が挙げられる。
-Polycyclic arylene group When the linking group A is a polycyclic arylene group, the number of condensed rings is preferably 2 to 4. Specifically, naphthalenediyl group, anthracenediyl group, phenanthrene diyl group, triphenylenediyl group and the like are preferable, and naphthalenediyl group is more preferable. At this time, the polycyclic aromatic linking group exemplified above may further have a substituent, and examples of the substituent include the examples of R 1 .
・アルキレン基
連結基Ａがアルキレン基であるとき、直鎖もしくは分岐のあるアルキレン基および環状アルキレン基のいずれでもよく、なかでも環状アルキレン基が好ましい。環状アルキレン基としては、炭素数４〜６の環状アルキレン基が好ましく、なかでも、シクロヘキサンジイル基が好ましい。連結基Ａがシクロヘキサンジイル基であるとき、本発明の化合物はその１，３−または１，４連結である下記式（１Ｂ）で表される構造であることが好ましい。但し、そのシクロヘキサン環については、トランス体、シス体、及び任意の割合であるシストランス混合物であってもよい。
-Alkylene group When the linking group A is an alkylene group, it may be either a linear or branched alkylene group or a cyclic alkylene group, and among them, a cyclic alkylene group is preferred. As the cyclic alkylene group, a cyclic alkylene group having 4 to 6 carbon atoms is preferable, and among them, a cyclohexanediyl group is preferable. When the linking group A is a cyclohexanediyl group, the compound of the present invention preferably has a structure represented by the following formula (1B), which is a 1,3- or 1,4-linkage thereof. However, the cyclohexane ring may be a trans isomer, a cis isomer, and a cis-trans mixture in an arbitrary ratio.
前記Ａがアラルキレン基であるとき、Ａは−Ｌａ（Ｃ６Ｈ４）Ｌａ−（Ｌａは炭素数１〜６のアルキレン基であることが好ましく、下記式（１Ｃ）の化合物であることが好ましい。
本発明の好ましい実施形態に係る利点について、さらに、後続する上記ポリマー合成反応との関係から述べる。本発明の好ましい実施形態のアシルトリアゾール誘導体は、ハロゲンフリーであることに加えて、その合成前駆体である酸クロリド化合物が、精製が難しい融点が低い固体酸クロリドないし沸点が高い液体酸クロリドをそのまま扱うことなく、これをトリアゾールにすることで適度な融点を持った固体とすることができる。しかもその反応性は、元の酸クロリドに匹敵する。この利点を活かす観点から、本発明のアシルトリアゾール化合物の前駆体である酸クロリド化合物は、融点が２０〜２００℃であることが好ましく、２０〜１００℃であることがより好ましい。または、沸点が常圧で２００℃以上であることが好ましい。沸点の上限は特にないが、３５０℃以下であることが好ましい。 Advantages according to a preferred embodiment of the present invention will be further described in relation to the subsequent polymer synthesis reaction. In addition to being halogen-free, the acyltriazole derivative according to a preferred embodiment of the present invention is an acid chloride compound that is a precursor of the synthesis of a solid acid chloride having a low melting point or a liquid acid chloride having a high boiling point, which is difficult to purify. Without handling, it is possible to obtain a solid having an appropriate melting point by using triazole. Moreover, its reactivity is comparable to the original acid chloride. From the viewpoint of taking advantage of this advantage, the acid chloride compound that is a precursor of the acyltriazole compound of the present invention preferably has a melting point of 20 to 200 ° C, more preferably 20 to 100 ° C. Alternatively, the boiling point is preferably 200 ° C. or higher at normal pressure. The upper limit of the boiling point is not particularly limited, but is preferably 350 ° C. or lower.
また、同様の観点からポリマー合成反応において用いられる反応溶媒に可溶であることが好ましい。その溶解度は特に限定されないが、２５℃で１０〜５０質量％であることが好ましく、１５〜３０質量％であることがより好ましい。ポリマー合成の反応溶媒としては、例えば、ＮＭＰ、ＤＭＦ，ＤＭＡＣ，ＭＥＫなどが用いられる。なお、上記ポリマーの合成反応については、特許文献４、５などを参照することができる。この溶解度を、単位体積当たりの質量で表すと、０．０１ｇ／ｍＬ以上であることが好ましく、０．１ｇ／ｍＬ以上であることがより好ましく、０．２ｇ／ｍＬ以上であることが特に好ましい。上限値は特にないが、１ｇ／ｍＬ以下であることが実際的である。 Moreover, it is preferable that it is soluble in the reaction solvent used in a polymer synthesis reaction from the same viewpoint. Although the solubility is not specifically limited, It is preferable that it is 10-50 mass% at 25 degreeC, and it is more preferable that it is 15-30 mass%. As a reaction solvent for polymer synthesis, for example, NMP, DMF, DMAC, MEK and the like are used. In addition, patent documents 4, 5 etc. can be referred for the synthesis reaction of the said polymer. When this solubility is expressed in terms of mass per unit volume, it is preferably 0.01 g / mL or more, more preferably 0.1 g / mL or more, and particularly preferably 0.2 g / mL or more. . Although there is no upper limit in particular, it is practical that it is 1 g / mL or less.
上記融点および溶媒溶解性の観点からは、式（１）の前記連結基Ａとしては、炭素数６〜１０のアルキレン基または炭素数８〜１２のアラルキレン基が好ましく、式（１Ｂ）および（１Ｃ）が特に好ましい。 From the viewpoint of the melting point and solvent solubility, the linking group A in the formula (1) is preferably an alkylene group having 6 to 10 carbon atoms or an aralkylene group having 8 to 12 carbon atoms, and the formulas (1B) and (1C Is particularly preferred.
融点、溶媒への溶解性についての一般則はないが、一般にパラ置換体よりメタ置換体の方が低融点であり、溶媒への溶解性が良い。たとえば、１，４−フェニレン基、即ちテレフタル酸ジトリアゾールは唯一の文献で知られた化合物であり、高分子量のポリマーを与えるモノマーとして報告されているが（Ｂｅｒ．１９５７年、９０巻、１３２６−１３３０ページ）、その後の展開、利用についての報告はない。それは、融点も高く加熱したＤＭＦにしか溶解せず、ポリマー合成における簡便性に欠けることが原因の一つであるとも解される（テレフタル酸ジトリアゾール、融点２３２℃（文献値））。
一方、本発明の好ましい実施形態に係る連結基Ａが１，３−フェニレン基または置換アリーレン基である新規なアシルトリアゾール化合物はパラ置換体よりも融点が低く、ＤＭＦ，ＮＭＰと言った非プロトン性極性溶媒のみならず、アセトン、ＭＥＫなどの溶媒にも可溶であり、ポリマー合成の条件に幅広く対応できる。
Although there is no general rule about melting point and solubility in a solvent, in general, a meta-substituted product has a lower melting point than a para-substituted product, and the solubility in a solvent is better. For example, the 1,4-phenylene group, i.e. ditriazole terephthalate, is the only compound known in the literature and has been reported as a monomer giving high molecular weight polymers (Ber. 1957, 90, 1326). 1330), and there is no report about subsequent development and use. It is also understood that it is only dissolved in heated DMF with a high melting point and is lacking in convenience in polymer synthesis (ditriazole terephthalate, melting point 232 ° C. (document value)).
On the other hand, the novel acyltriazole compound in which the linking group A according to a preferred embodiment of the present invention is a 1,3-phenylene group or a substituted arylene group has a lower melting point than that of the para-substituted product, and is aprotic such as DMF and NMP. It is soluble not only in polar solvents but also in solvents such as acetone and MEK, and can cope with a wide range of polymer synthesis conditions.
ＤＭＦへの２５℃における溶解度
テレフタル酸ジトリアゾール ０．００２ｇ／ｍＬ
イソフタル酸ジトリアゾール ０．４ｇ／ｍＬ
Solubility in DMF at 25 ° C. Ditriazole terephthalate 0.002 g / mL
Diphthalazole isophthalate 0.4g / mL
［製造方法］
上記新規アシルトリアゾール誘導体は、以下の製造方法で好適に製造することができる。すなわち、本発明の好ましい実施形態は、下記式（２）で表されるジカルボン酸化合物を下記式（３）で表されるジカルボン酸ジクロリド化合物に変換したのち、当該ジカルボン酸クロリド化合物を単離または単離せずに１，２，４−トリアゾールを反応させ、下記式（１）で表される化合物を生成させるアシルトリアゾール誘導体の製造方法を提供する。
The novel acyltriazole derivative can be suitably produced by the following production method. That is, in a preferred embodiment of the present invention, a dicarboxylic acid compound represented by the following formula (2) is converted into a dicarboxylic acid dichloride compound represented by the following formula (3), and then the dicarboxylic acid chloride compound is isolated or Provided is a method for producing an acyltriazole derivative in which 1,2,4-triazole is reacted without isolation to produce a compound represented by the following formula (1).
すなわち、より一般化して言うと、前記誘導体は、カルボン酸クロリドと１，２，４−トリアゾールを反応させることにより上記新規なカルボン酸アシルトリアゾールを製造することができる。その際、生成する塩化水素を確実に除去するために当量以上の塩基を使用することが好ましい。塩基としては、有機塩基、無機塩基のいずれの使用も可能である。有機塩基としては、トリエチルアミン、ピリジンなどの３級アミンが好ましい。あるいは、１，２，４−トリアゾールを塩基として過剰量用いることもできる。無機塩基としては、水酸化ナトリウム、炭酸ナトリウム、炭酸水素ナトリウムなどが好適に挙げられる。但し、反応は無水条件で行うことが好ましい。 That is, more generally speaking, the derivative can produce the novel carboxylic acyltriazole by reacting carboxylic acid chloride with 1,2,4-triazole. At that time, it is preferable to use an equivalent or more base in order to reliably remove the generated hydrogen chloride. As the base, either an organic base or an inorganic base can be used. As the organic base, tertiary amines such as triethylamine and pyridine are preferable. Alternatively, an excess amount of 1,2,4-triazole can be used as a base. Preferable examples of the inorganic base include sodium hydroxide, sodium carbonate, sodium hydrogen carbonate and the like. However, the reaction is preferably performed under anhydrous conditions.
上記の点を考慮すると、１，２，４−トリアゾールをカルボン酸化合物の当量に対して、１〜２倍量で投入することが好ましい。１，２，４−トリアゾールを塩基としても利用する場合には、前記モル当量に対して２〜４倍量で投入することが好ましい。 Considering the above points, it is preferable to add 1,2,4-triazole in an amount of 1 to 2 times the equivalent of the carboxylic acid compound. When 1,2,4-triazole is also used as a base, it is preferably added in an amount 2 to 4 times the molar equivalent.
カルボン酸ジクロリドの種類としては特に限定されないが、目的とするポリマー合成に応じ所望の構造をもつものを採用すればよい。上記の例で示すと、ＨＯＯＣ−Ａ−ＣＯＯＨ（式Ｂ）で表されるものが好ましい。ここでＡは前記式（１）と同義である。 Although it does not specifically limit as a kind of carboxylic acid dichloride, What is necessary is just to employ | adopt what has a desired structure according to the target polymer synthesis | combination. When it shows in said example, what is represented by HOOC-A-COOH (Formula B) is preferable. Here, A is synonymous with the formula (1).
カルボン酸ジクロリドと１，２，４−トリアゾールの反応は通常溶媒を用いるが、その溶媒としてはそれぞれの化合物と反応しないものなら特に制限はない。トルエン、クロロトルエン、クロロベンゼン、ジクロロメタン、アセトン、メチルエチルケトン、テトラヒドロフラン、ＤＭＦ、ＮＭＰなどが挙げられる。反応後、水を加え析出したカルボン酸ジアシルトリアゾールをろ過、水洗、乾燥するか、有機溶媒で抽出、水洗、溶媒留去することで新規なカルボン酸ジアシルトリアゾールを得ることができる。本発明のアシルトリアゾール誘導体の特徴として、水処理することが可能であることが挙げられる。それにより、ハロゲンを含む無機物、有機塩を取り除くことができる。水処理に使用できる水は中性であることが好ましい。アミンなどの求核剤との反応性がアシルクロリド誘導体に匹敵するにも関わらず、中性水との反応に耐えるという利点を有する。 The reaction of carboxylic acid dichloride and 1,2,4-triazole usually uses a solvent, but the solvent is not particularly limited as long as it does not react with each compound. Examples include toluene, chlorotoluene, chlorobenzene, dichloromethane, acetone, methyl ethyl ketone, tetrahydrofuran, DMF, and NMP. After the reaction, water is added to the precipitated carboxylic acid diacyltriazole, which is filtered, washed with water and dried, or extracted with an organic solvent, washed with water and evaporated to obtain a novel carboxylic acid diacyltriazole. A feature of the acyltriazole derivative of the present invention is that it can be treated with water. Thereby, inorganic substances and organic salts containing halogen can be removed. The water that can be used for water treatment is preferably neutral. Despite its reactivity with nucleophiles such as amines comparable to acyl chloride derivatives, it has the advantage of withstanding reaction with neutral water.
用いるカルボン酸ジクロリドの入手方法に制限はないが、相当するカルボン酸をカルボン酸ジクロリドに変換したのち、単離することなく１，２，４−トリアゾールと反応させることもできる。これにより、各種カルボン酸を簡便にトリアゾール活性エステルに変換できる。 Although there is no restriction | limiting in the acquisition method of carboxylic acid dichloride to be used, After converting a corresponding carboxylic acid into carboxylic acid dichloride, it can also make it react with 1,2,4- triazole, without isolating. Thereby, various carboxylic acids can be easily converted into triazole active esters.
前記カルボン酸ジクロリドと１、２、４−トリアゾールとの反応温度は特に限定されないが、−１０〜５０℃であることが好ましく、５〜２０℃であることがより好ましい。 The reaction temperature between the carboxylic acid dichloride and 1,2,4-triazole is not particularly limited, but is preferably −10 to 50 ° C., and more preferably 5 to 20 ° C.
カルボン酸をカルボン酸ジクロリドに変換する既知の方法として、塩化チオニル、３塩化リン、オキシ塩化リン、蓚酸ジクロリド、ホスゲンなどがあるが、いずれも大量使用においては排水、廃棄物、毒性、価格などの問題点を含んでおり、新たな方法が求められていた。本発明者らは、フタル酸ジクロリドを塩素化剤とする新たなカルボン酸ジクロリドの製造方法を先に開発した（特願２０１１−１７４０７４）。本発明は、フタル酸ジクロリド（ＯＰＣ）を用いるビルスマイヤー試薬を用い、カルボン酸をカルボン酸ジクロリドに安全かつ安価に変換し、続いて新規なカルボン酸ジアシルトリアゾールを製造するルートをも開示する。 Known methods for converting carboxylic acid to carboxylic acid dichloride include thionyl chloride, phosphorus trichloride, phosphorus oxychloride, oxalic acid dichloride, and phosgene, all of which include wastewater, waste, toxicity, price, etc. There was a problem and a new method was sought. The inventors of the present invention have previously developed a new method for producing carboxylic acid dichloride using phthalic acid dichloride as a chlorinating agent (Japanese Patent Application No. 2011-174074). The present invention also discloses a route for the safe and inexpensive conversion of carboxylic acid to carboxylic acid dichloride using a Vilsmeier reagent using phthalic acid dichloride (OPC), followed by the preparation of a novel carboxylic acid diacyltriazole.
本発明者は、前記１，２，４−トリアゾール誘導体が、１，３−イミダゾール誘導体に比べてアミンまたはアルコールとの反応性が高いと予想し、実施例によってその推論が正しいことを明らかとした。その作用原理について前記推論の根拠と併せて下記に述べる。
ＢｏｒｄｗｅｌｌのｐＫａ表（Ｆ．Ｇ．Ｂｏｒｄｗｅｌｌ Ａｃｃ．Ｃｈｅｍ．Ｒｅｓ．１９８８，２１，４５６―４６３．）によると、ＤＭＳＯ中での１，３−イミダゾールはｐＫａ１８．６であり、１，２，４−トリアゾールはｐＫａ１４．８とある。すなわち、トリアゾールの方が１００００倍酸性度が高いことになり、共役塩基としてのトリゾールアニオンがイミダゾールアニオンに比べて脱離能が高いと予想される。この高いトリアゾール部位の脱離能が、前記ポリマー合成反応における高い反応性につながったと考えられる。
The present inventor predicted that the 1,2,4-triazole derivative is more reactive with an amine or alcohol than the 1,3-imidazole derivative, and clarified that the inference is correct according to the examples. . The operation principle will be described below together with the reasoning of the inference.
According to Bordwell's pKa table (FG Bordwell Acc. Chem. Res. 1988, 21, 456-463.), 1,3-imidazole in DMSO is pKa 18.6, 1,2,4- The triazole is pKa14.8. That is, triazole is 10,000 times higher in acidity, and it is expected that the trizole anion as a conjugate base has higher elimination ability than the imidazole anion. This high triazole moiety elimination ability is thought to have led to high reactivity in the polymer synthesis reaction.
本発明の好ましい実施形態に係るアシルトリアゾール誘導体からなるモノマーは、ポリカーボネートなどの有用な重合体の製造に好適に用いることができる。例えば、式（１）の連結基Ａをビスフェノール連結基とすればポリカーボネート樹脂を得ることができる。あるいは、ジアミン化合物と共重合させてポリアミド樹脂を得ることができる。その利点は、その化学構造から分かるとおり、塩素を可及的に排除できることにある。ポリカーボネートやポリアミドの製造において、品質の劣化要因となり、また環境に影響をあたえる塩素は抑制されることが望ましく、その抑制・排除は技術課題となっている。本発明のアシルトリアゾール誘導体によれば、そもそも塩素をその原料に含むことがないため、効果的に塩素を排除した樹脂合成を可能とする。なお、ポリカーボネート樹脂の製造については、例えば、特開昭６１−２５００２６号公報等を参照することができる。 A monomer composed of an acyltriazole derivative according to a preferred embodiment of the present invention can be suitably used for producing a useful polymer such as polycarbonate. For example, if the linking group A in the formula (1) is a bisphenol linking group, a polycarbonate resin can be obtained. Alternatively, a polyamide resin can be obtained by copolymerization with a diamine compound. The advantage is that chlorine can be eliminated as much as possible, as can be seen from its chemical structure. In the production of polycarbonate and polyamide, it is desirable to suppress chlorine, which is a factor of deterioration of quality and has an influence on the environment, and its suppression and elimination is a technical problem. According to the acyltriazole derivative of the present invention, since chlorine is not originally contained in the raw material, resin synthesis in which chlorine is effectively eliminated is enabled. For the production of polycarbonate resin, reference can be made to, for example, JP-A No. 61-250026.
以下に、本発明について実施例に基づきさらに詳細に説明するが、本発明がこれに限定して解釈されるものではない。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not construed as being limited thereto.
実施例１
ジクロロメタン３５ｍＬとＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）６ｍＬに１，２，４−トリアゾール２．８ｇ（４０．６ミリモル）を溶解した。そこに４，４’−オキシビス安息香酸クロリド（ｍｐ８８−８９℃）２．９ｇ（９．８ミリモル）をジクロロメタン１５ｍＬとＤＭＦ０．１ｍＬに溶解した液を室温で滴下した。最初の１滴で白濁した。室温で３時間攪拌したのち、水１００ｍＬを加え分液、ジクロロメタン層を水で３回洗浄したのち、無水硫酸ナトリウムで乾燥した。溶媒を減圧留去後、８０℃で１時間真空乾燥し白色の４，４’−ビフェニルエーテルジカルボニルジトリアゾール（ＯＢＢＯＴｒ）２．４５ｇ（収率６９．４％）を得た。
ｍｐ１６４．０−１６４．４℃ （Ｂｕｃｈｉ融点測定器 Ｂ−５４５）
ＩＲ（ＫＢｒ）：１７０５ｃｍ−１（ＣＯ）．
ＧＣ−ＭＳ：ｍ／ｚ＝３６０（Ｍ＋，相対値１８％），２９２（Ｍ＋−Ｔｒ，１００％）．
１Ｈ−ＮＭＲ（ＣＤＣｌ３）：δ＝７．２２（ｄ、Ｊ＝６．９Ｈｚ、４Ｈ），８．１４（ｓ，２Ｈ），８．３８（ｄ，Ｊ＝６．９Ｈｚ，４Ｈ），９．１２（ｓ，２Ｈ）．
１３Ｃ−ＮＭＲ（ＣＤＣｌ３）：１１９，１２５，１３５，１４６，１４６，１５４，１６１
Example 1
In 35 mL of dichloromethane and 6 mL of N, N-dimethylformamide (DMF), 2.8 g (40.6 mmol) of 1,2,4-triazole was dissolved. A solution prepared by dissolving 2.9 g (9.8 mmol) of 4,4′-oxybisbenzoyl chloride (mp 88-89 ° C.) in 15 mL of dichloromethane and 0.1 mL of DMF was added dropwise thereto at room temperature. It became cloudy with the first drop. After stirring at room temperature for 3 hours, 100 mL of water was added to separate the layers, and the dichloromethane layer was washed 3 times with water and then dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, it was vacuum-dried at 80 ° C. for 1 hour to obtain 2.45 g (yield 69.4%) of white 4,4′-biphenyl ether dicarbonylditriazole (OBBOTr).
mp164.0-164.4 ° C. (Buchi melting point meter B-545)
IR (KBr): 1705 cm < -1 > (CO).
GC-MS: m / z = 360 (M + , relative value 18%), 292 (M + -Tr, 100%).
1 H-NMR (CDCl 3 ): δ = 7.22 (d, J = 6.9 Hz, 4H), 8.14 (s, 2H), 8.38 (d, J = 6.9 Hz, 4H), 9.12 (s, 2H).
13 C-NMR (CDCl 3 ): 119, 125, 135, 146, 146, 154, 161
実施例２
ＤＭＦ２０ｇを２−クロロトルエン（ＯＣＴ）５０ｍＬに溶解し、フタル酸ジクロリド（ＯＰＣと略す）１９．４ｇを加え６０℃で２時間攪拌した。析出したビルスマイヤー試薬（ＶＲ）を窒素雰囲気下、減圧ろ過により採取、ＯＣＴ５０ｍＬで洗浄した。ＶＲ試薬を再びフラスコに移し、４，４’−オキシビス安息香酸１０．２ｇ（３９．５ミリモル）とＯＣＴ５０ｍＬを加え６０℃で２時間攪拌した。反応液が完全に透明になったところで反応終了とした。ＯＣＴ層に１，２，４−トリアゾール１０．９７ｇのＮＭＰ２５ｍＬ溶液を氷冷下１５分で滴下、さらに室温で１時間半攪拌した。水３００ｍＬとアセトン２０ｍＬを加え、結晶をろ取、水３００ｍＬで洗浄した。９０℃減圧乾燥後、結晶を９０ｍＬの１，２−ジメトキシエタンで再結晶した。４．８ｇの４，４’−ビフェニルエーテルジカルボニルジトリアゾール（ＯＢＢＯＴｒ）を収率５３％で得た。
ｍｐ１６６．６−１６７．１℃
ＧＣＭＳスペクトルは実施例１の化合物と一致した。
Example 2
20 g of DMF was dissolved in 50 mL of 2-chlorotoluene (OCT), 19.4 g of phthalic acid dichloride (abbreviated as OPC) was added, and the mixture was stirred at 60 ° C. for 2 hours. The deposited Vilsmeier reagent (VR) was collected by filtration under reduced pressure in a nitrogen atmosphere and washed with 50 mL of OCT. The VR reagent was again transferred to the flask, 10.2 g (39.5 mmol) of 4,4′-oxybisbenzoic acid and 50 mL of OCT were added, and the mixture was stirred at 60 ° C. for 2 hours. The reaction was terminated when the reaction solution became completely transparent. To the OCT layer, a solution of 10.97 g of 1,2,4-triazole in 25 mL of NMP was added dropwise over 15 minutes under ice cooling, and the mixture was further stirred at room temperature for 1.5 hours. 300 mL of water and 20 mL of acetone were added, and the crystals were collected by filtration and washed with 300 mL of water. After drying at 90 ° C. under reduced pressure, the crystals were recrystallized from 90 mL of 1,2-dimethoxyethane. 4.8 g of 4,4′-biphenyl ether dicarbonylditriazole (OBBOTr) was obtained with a yield of 53%.
mp 166.6-167.1 ° C
The GCMS spectrum was consistent with the compound of Example 1.
比較例１
実施例１の１，２，４−トリアゾールの代わりに１，３―イミダゾール２．８ｇ（４１．２ミリモル）をジクロロメタン１５ｍＬに溶解し４，４’−オキシビス安息香酸クロリドと同じように反応した。４，４’−ビフェニルエーテルジカルボニルジイミダゾール（ＯＢＢＯＩｍ）を３．２０ｇ（収率９１．２％）得た。これを試験例１で使用した。
ｍｐ１７７．２−１７８．３℃
ＧＣ−ＭＳ：ｍ／ｚ＝３５８（Ｍ＋，相対値＜１％）、２９１（Ｍ＋−Ｉｍ，１００％）
Instead of 1,2,4-triazole of Example 1, 2.8 g (41.2 mmol) of 1,3-imidazole was dissolved in 15 mL of dichloromethane and reacted in the same manner as 4,4′-oxybisbenzoic acid chloride. 3.20 g (yield 91.2%) of 4,4′-biphenyl ether dicarbonyldiimidazole (OBBOIm) was obtained. This was used in Test Example 1.
mp 177.2-178.3 ° C
GC-MS: m / z = 358 (M + , relative value <1%), 291 (M + −Im, 100%)
実施例３
ナフタレン−２，６−ジカルボニルジクロリド２．５３ｇ（１０ミリモル）をジクロロメタン３０ｍＬとＤＭＦ２ｍＬに加熱して溶解させた。そこに、１，２，４−トリアゾール２．８０ｇ（４０ミリモル）のＤＭＦ８ｍＬ溶液を滴下した。全量加え５０℃で１時間攪拌後、水１００ｍＬを加え結晶をろ取、水１００ｍＬ＋アセトン１０ｍＬで洗浄、もう一度水１００ｍＬで洗浄した。１０５℃で２時間真空乾燥し２．７ｇ（収率８５％）の粗ナフタレン−２，６−ジカルボニルジトリアゾールを得た。ｍｐ２４２−２４４℃。
ＧＣ−ＭＳ：ｍ／ｚ＝３１８（Ｍ＋，相対値２６％）、２５０（Ｍ＋−Ｔｒ，１００％）、１５４、１２６．
ＮＭＰ５０ｍＬで再結晶し、融点２５２−２５４℃の純品を得た。
Naphthalene-2,6-dicarbonyl dichloride (2.53 g, 10 mmol) was dissolved in 30 mL of dichloromethane and 2 mL of DMF by heating. Thereto was added dropwise a solution of 2.80 g (40 mmol) of 1,2,4-triazole in 8 mL of DMF. After adding the entire amount and stirring at 50 ° C. for 1 hour, 100 mL of water was added, and the crystals were collected by filtration, washed with 100 mL of water + 10 mL of acetone, and once again with 100 mL of water. Vacuum drying at 105 ° C. for 2 hours gave 2.7 g (yield 85%) of crude naphthalene-2,6-dicarbonylditriazole. mp 242-244 ° C.
GC-MS: m / z = 318 (M + , relative value 26%), 250 (M + -Tr, 100%), 154, 126.
Recrystallization was performed with 50 mL of NMP to obtain a pure product having a melting point of 252-254 ° C.
実施例４
ＤＭＦ９０．１ｇとトルエン２３０ｍＬを５０℃のオイルバス中で攪拌した中へＯＰＣ８３．３ｇ（０．４１モル）を５分間で滴下した。３時間後にグラスフィルターにて減圧下、窒素雰囲気下でビルスマイヤー試薬の結晶をろ取、トルエン１００ｍＬで２回、ヘキサン１００ｍＬで１回洗浄した。結晶を４０℃で１時間真空乾燥した。得られたビルスマイヤー試薬の得量４４．５ｇ（収率８５％）。
結晶ろ液から溶媒を回収し残さをトルエンーヘキサン１：４の５０ｍＬ溶液でトリチュレートし、結晶ろ取、トルエンーヘキサン１：４の５０ｍＬ溶液で洗浄後、乾燥するとほぼ純粋な無水フタル酸５３．８ｇ（８８．７％）を回収した。融点１３１．７℃（文献値１３１−１３３℃：Ａｌｄｒｉｃｈカタログ）。
Example 4
While stirring 90.1 g of DMF and 230 mL of toluene in an oil bath at 50 ° C., 83.3 g (0.41 mol) of OPC was added dropwise over 5 minutes. After 3 hours, the crystals of the Vilsmeier reagent were collected by filtration with a glass filter under a reduced pressure and a nitrogen atmosphere, and washed twice with 100 mL of toluene and once with 100 mL of hexane. The crystals were vacuum dried at 40 ° C. for 1 hour. The amount of the obtained Vilsmeier reagent was 44.5 g (yield 85%).
The solvent was recovered from the crystal filtrate, and the residue was triturated with a 50 mL solution of toluene-hexane 1: 4. The crystal was filtered, washed with a 50 mL solution of toluene-hexane 1: 4, and dried to obtain almost pure phthalic anhydride 53. 8 g (88.7%) was recovered. Melting point 131.7 ° C. (literature value 131-133 ° C .: Aldrich catalog).
上記で合成したビルスマイヤー試薬３．１ｇ（２４ミリモル）をトルエン３０ｍＬに懸濁し、トランス−１，４−シクロヘキサンジカルボン酸（東京化成試薬）１．６ｇ（９．３ミリモル）を粉末のまま加え、室温（１８℃）で０．２５時間、さらに３５℃のオイルバス中で０．２５時間攪拌した。下層の褐色オイルをデカンテーションで取り除き、トランス−１，４−シクロヘキサンジカルボン酸ジクロリドを含むトルエン溶液を得た。これに１，２，４−トリアゾール２．６ｇ（３７．７ミリモル）をＤＭＦ１０ｍＬに溶解して一度に加えた。直ちに、白色結晶が現れ少し発熱した。室温で４０分間攪拌後、水１００ｍＬを加え析出した結晶をろ取、水洗後７０℃で１時間真空乾燥し白色のトランス−１，４−シクロヘキサンジカルボニルジトリアゾールを２．４ｇ（９３．８％収率）得た。
ｍｐ２４１．０−２４２．４℃（分解）
ＧＣＭＳ（ｄｉｒｅｃｔ）：ｍ／ｚ＝２０６（Ｍ＋−ＴｒＨ）．
ＧＣＭＳ（Ｅｔ２ＮＨ処理）：ｍ／ｚ＝２８２（Ｍ＋、相対値２８％）１８２（５６％）、１００（７２％）、７２（１００％）。
上記実施例は、トランス−１，４−シクロヘキサンジカルボン酸ジクロリドを単離することなくトリアゾール誘導体に導いたが、融点６４−６６℃のトランス−１，４−シクロヘキサンジカルボン酸ジクロリド（文献値融点 ６４−６７℃：Ｓｙｎｔｈｅｓｉｓ１９９１，４４１−４４２）を単離したのち、トランス−１，４−シクロヘキサンジカルボニルジトリアゾールとすることもできた。
mp 241.0-242.4 ° C. (decomposition)
GCMS (direct): m / z = 206 (M <+ > - TrH).
GCMS (Et2NH treatment): m / z = 282 (M + , relative value 28%) 182 (56%), 100 (72%), 72 (100%).
In the above examples, trans-1,4-cyclohexanedicarboxylic acid dichloride was led to a triazole derivative without isolation, but trans-1,4-cyclohexanedicarboxylic acid dichloride having a melting point of 64-66 ° C. (literature value melting point 64- 67 ° C .: Synthesis 1991, 441-442) was isolated and then trans-1,4-cyclohexanedicarbonylditriazole could be obtained.
実施例５
実施例４と同様にして、１，４−シクロヘキサンジカルボン酸異性体混合物（トランス：シス＝約１：３）を用いて白色の１，４−シクロヘキサンジカルボニルジトリアゾール結晶（トランス：シス＝１：３）を定量的収率で得た。
ＧＣＭＳでトランス体およびシス体の構造をそれぞれ確認した。トランス体は実施例４で得たＧＣＭＳと一致した。
トランス体：ｍ／ｚ＝２０６（相対値１３％）、１７８（１０％）、１３７（５０％）、１０９（３５％）、８１（９７％）、７０（ベースピーク）。
シス体：ｍ／ｚ＝２０６（相対値４３％）、１７８（１６％）、１０９（３８％）、８１（ベースピーク）、７０（９２％）。
Example 5
In the same manner as in Example 4, a 1,4-cyclohexanedicarboxylic acid isomer mixture (trans: cis = about 1: 3) was used and white 1,4-cyclohexanedicarbonylditriazole crystals (trans: cis = 1: 3) was obtained in quantitative yield.
The structures of trans and cis isomers were confirmed by GCMS. The trans isomer was consistent with the GCMS obtained in Example 4.
Trans isomer: m / z = 206 (relative value 13%), 178 (10%), 137 (50%), 109 (35%), 81 (97%), 70 (base peak).
Cis isomer: m / z = 206 (relative value 43%), 178 (16%), 109 (38%), 81 (base peak), 70 (92%).
実施例６
ビルスマイヤー試薬５．８ｇ（４５．３ミリモル）をトルエン４０ｍＬに懸濁し、１，４−ベンゼンジ酢酸３．８８ｇ（２０ミリモル）を加え、３５−４０℃で１５分間攪拌した。トルエン溶液を分離し、トルエンを減圧留去し相当する酸クロリド４．４８ｇ（粗収率９７．４％）の淡黄色結晶を得た。ＧＣ−ＭＳ：ｍ／ｚ＝２３０（Ｍ＋）．
これをシクロヘキサン４０ｍＬから再結晶し、４．０ｇ（８７％）の１，４−ベンゼンジアセチルクロリドを得た。ｍｐ６５−６７℃（文献値、ｍｐ６６−６６．５℃：Ｊ．Ｏｒｇ．Ｃｈｅｍ．１９５３年１８巻７０７−７１４頁）。ＧＣ−ＭＳ（ジエチルアミン処理）：ｍ／ｚ＝３０４（Ｍ＋、相対値１７％），１００（ベースピーク）、７２（相対値３８％）．
上記、１，４−ベンゼンジアセチルクロリド２．１ｇ（９．１ミリモル）をジクロロメタン１５ｍＬとＤＭＦ２ｍＬの混合溶液に溶解し、１，２，４−トリアゾール２．６ｇ（３７．３ミリモル）をＤＭＦ１０ｍＬに溶解した液を室温で加えた。１時間攪拌後、水１５０ｍＬに空け、結晶をろ取、水洗、乾燥し２．０ｇ（７４％）の１，４−ベンゼンジアセチルトリアゾールを得た。ｍｐ１９６．２−１９６．８℃。
１，４−ベンゼンジアセチルトリアゾールの一部をジクロロメタンに溶解しジエチルアミンを加え、室温で５分後にＧＣ−ＭＳを測定した。その結果、全量がアミド誘導体に変化しており、１，４−ベンゼンジアセチルクロリドをジエチルアミン処理したＧＣＭＳと完全に一致した。ｍ／ｚ＝３０４（Ｍ＋）
5.8 g (45.3 mmol) of Vilsmeier reagent was suspended in 40 mL of toluene, 3.88 g (20 mmol) of 1,4-benzenediacetic acid was added, and the mixture was stirred at 35-40 ° C. for 15 minutes. The toluene solution was separated, and toluene was distilled off under reduced pressure to obtain 4.48 g (crude yield 97.4%) of pale yellow crystals of the corresponding acid chloride. GC-MS: m / z = 230 (M <+> ).
This was recrystallized from 40 mL of cyclohexane to obtain 4.0 g (87%) of 1,4-benzenediacetyl chloride. mp 65-67 ° C. (literature value, mp 66-66.5 ° C .: J. Org. Chem. 1953, 18: 707-714). GC-MS (diethylamine treatment): m / z = 304 (M + , relative value 17%), 100 (base peak), 72 (relative value 38%).
Dissolve 2.1 g (9.1 mmol) of 1,4-benzenediacetyl chloride in a mixed solution of 15 mL of dichloromethane and 2 mL of DMF, and dissolve 2.6 g (37.3 mmol) of 1,2,4-triazole in 10 mL of DMF. The solution was added at room temperature. After stirring for 1 hour, the solution was poured into 150 mL of water, and the crystals were collected by filtration, washed with water and dried to obtain 2.0 g (74%) of 1,4-benzenediacetyltriazole. mp 196.2-196.8 ° C.
A part of 1,4-benzenediacetyltriazole was dissolved in dichloromethane, diethylamine was added, and GC-MS was measured after 5 minutes at room temperature. As a result, the total amount was changed to an amide derivative, which was completely consistent with GCMS in which 1,4-benzenediacetyl chloride was treated with diethylamine. m / z = 304 (M + )
実施例７
濃硫酸２５ｍＬを水３５ｍＬで薄め、１，３−ベンゼンジアセトニトリル ２４ｇを加え、１時間３０分リフラックスした。氷水２００ｍＬに空けて析出した結晶をろ取、水洗した。減圧下１００℃で１時間乾燥し２７ｇの１，３−ベンゼンジ酢酸を得た。ＧＣＭＳ：ｍ／ｚ＝１９４（Ｍ＋），１４９、１０４（ベースピーク）。
ビルスマイヤー試薬 ３．８ｇ（２９．７ミリモル）をジクロロメタン ３０ｍＬに懸濁し、上記で合成した１，３−ベンゼンジ酢酸 ２．８ｇ（１４．４ミリモル）を加えた。反応液は直ちに均一となった。室温で１０分後に溶媒を減圧留去すると３．４ｇの油状物質が得られた。このものをＧＣＭＳにかけると、酸クロリドに相当するｍ／ｚ＝２３０のピークがブロードに観測され、同時に脱塩化水素したケテン体に相当するピークも観測された。そこで、ジエチルアミンで処理しアミド体に誘導しＧＣＭＳを測定すると単一ピークとなりｍ／ｚ＝３０４（Ｍ＋）を示し、１，３−ベンゼンジアセチルクロリドが定量的に生成していることを確認した。
上記１、３−ベンゼンジアセチルクロリドの全量を無水ＴＨＦに溶解し、１，２，４−トリアゾール ４．０ｇ（５８．０ミリモル）を添加し７０℃で０．５時間撹拌した。冷却後、結晶をろ過で取り除き、ＴＨＦ溶液を濃縮、ジクロロメタンに溶解し水で洗った。芒硝で乾燥後、溶媒を留去すると３．７ｇの無色透明のオイルが得られ、放置すると結晶化した。これを分析すると、１，３−ベンゼンジアセチルトリアゾールであった。収率は１，３−ベンゼンジ酢酸からの通算収率で８７％であった。ＧＣＭＳ：ベースピーク２２７（Ｍ−ＴｒＨ）。融点９３〜９４℃（イソプロピルアルコールから再結晶）
25 mL of concentrated sulfuric acid was diluted with 35 mL of water, 24 g of 1,3-benzenediacetonitrile was added, and the mixture was refluxed for 1 hour and 30 minutes. Crystals deposited in 200 mL of ice water were collected by filtration and washed with water. It dried at 100 degreeC under pressure reduction for 1 hour, and 27 g of 1, 3- benzenediacetic acid was obtained. GCMS: m / z = 194 (M <+> ), 149, 104 (base peak).
3.8 g (29.7 mmol) of Vilsmeier reagent was suspended in 30 mL of dichloromethane, and 2.8 g (14.4 mmol) of 1,3-benzenediacetic acid synthesized above was added. The reaction solution became homogeneous immediately. After 10 minutes at room temperature, the solvent was distilled off under reduced pressure to obtain 3.4 g of an oily substance. When this was subjected to GCMS, a peak at m / z = 230 corresponding to acid chloride was observed broadly, and at the same time, a peak corresponding to dehydrochlorinated ketene was also observed. Then, when it treated with diethylamine, it induced | guided | derived to the amide body and GCMS was measured, it became a single peak, showed m / z = 304 (M <+> ), and confirmed that the 1, 3- benzene diacetyl chloride was producing | generating quantitatively. .
The total amount of 1,3-benzenediacetyl chloride was dissolved in anhydrous THF, 4.0 g (58.0 mmol) of 1,2,4-triazole was added, and the mixture was stirred at 70 ° C. for 0.5 hour. After cooling, the crystals were removed by filtration, the THF solution was concentrated, dissolved in dichloromethane, and washed with water. After drying with sodium sulfate, the solvent was distilled off to obtain 3.7 g of a colorless and transparent oil, which crystallized on standing. When this was analyzed, it was 1,3-benzenediacetyltriazole. The yield was 87% in total yield from 1,3-benzenediacetic acid. GCMS: base peak 227 (M-TrH). Melting point 93-94 ° C (recrystallized from isopropyl alcohol)
実施例８
イソフタル酸クロリド３０．７ｇ（０．１５モル）のジクロロメタン２５ｍＬ溶液に、１，２，４−トリアゾール４２．２ｇ（０．６１モル）のジクロロメタン２００ｍＬ溶液を室温で３０分かけ加えた。そのまま、１時間撹拌を続け水１００ｍＬで希釈し、有機層を分液、２００ｍＬの水で２回洗浄した。芒硝で乾燥後、溶媒を留去し、イソフタロイルジトリアゾール３９．７ｇ（９８．８％収率）を得た。
融点１１９．０〜１１９．４℃。ＧＣＭＳ：ｍ／ｚ＝２００（ベースピークＭ＋−Ｔｒ）
イソフタロイルジトリアゾールの一部をジクロロメタンに溶解しジエチルアミンを過剰量加え、直ちにＧＣＭＳを測定した。その結果、全量がイソフタロイルジエチルアミドに変化していた。ｍ／ｚ＝２７６（Ｍ＋）
To a solution of 30.7 g (0.15 mol) of isophthalic acid chloride in 25 mL of dichloromethane, a solution of 42.2 g (0.61 mol) of 1,2,4-triazole in 200 mL of dichloromethane was added at room temperature over 30 minutes. The stirring was continued for 1 hour, and the mixture was diluted with 100 mL of water, and the organic layer was separated and washed twice with 200 mL of water. After drying with sodium sulfate, the solvent was distilled off to obtain 39.7 g (98.8% yield) of isophthaloyl ditriazole.
Melting point 119.0-119.4C. GCMS: m / z = 200 (base peak M + -Tr)
A part of isophthaloyl ditriazole was dissolved in dichloromethane, an excess amount of diethylamine was added, and GCMS was immediately measured. As a result, the total amount was changed to isophthaloyl diethylamide. m / z = 276 (M + )
実施例９ （カルボン酸からのワンポット合成）
１，４―ベンゼン２酢酸３２．８ｇ（０．１８モル）を２−クロロトルエン１２０ｍＬに懸濁し、ＤＭＦ２４ｍＬ（約０．３６モル）を加えた。そこに、フタロイルクロリド７３ｇ（０．３６モル）を滴下し７０℃で撹拌すると４５分で均一溶液となった。５５℃まで冷却し１，２，４−トリアゾール５１．６ｇ（０．７５モル）をＤＭＦ１８０ｍＬに溶解した液を２０分かけて滴下した。３０℃まで自然冷却し析出した結晶をろ取、２５０ｍＬの水で２回結晶を洗い、８０℃で２時間減圧乾燥した。１，４−ベンゼンジアセチルトリアゾールの淡黄色結晶３５ｇ（通算取率６６％）を得た。融点１９４．５℃。
ＧＣＭＳ：ｍ／ｚ＝２２７（Ｍ＋−ＴｒＨ），１５８（ベースピーク）。
実施例６で合成した１，４−ベンゼンジアセチルトリアゾールのＧＣＭＳと完全に一致した。
Example 9 (One-pot synthesis from carboxylic acid)
1,4-Benzenediacetic acid 32.8 g (0.18 mol) was suspended in 2-chlorotoluene 120 mL, and DMF 24 mL (about 0.36 mol) was added. Thereto, 73 g (0.36 mol) of phthaloyl chloride was added dropwise and stirred at 70 ° C. to obtain a uniform solution in 45 minutes. After cooling to 55 ° C., a solution prepared by dissolving 51.6 g (0.75 mol) of 1,2,4-triazole in 180 mL of DMF was added dropwise over 20 minutes. The crystals that were naturally cooled to 30 ° C. were collected by filtration, washed twice with 250 mL of water, and dried under reduced pressure at 80 ° C. for 2 hours. 35 g of light yellow crystals of 1,4-benzenediacetyltriazole (total rate of 66%) were obtained. Melting point 194.5 ° C.
GCMS: m / z = 227 (M <+ > - TrH), 158 (base peak).
Completely consistent with the GCMS of 1,4-benzenediacetyltriazole synthesized in Example 6.
実施例１０ （カルボン酸からの一貫合成）
１，４−シクロヘキサンジカルボン酸異性体混合物（トランス／シス＝約２／８）２５．８ｇ（０．１５モル）にシクロヘキサン１００ｍＬ，ＤＭＦ４ｍＬ，ＯＰＣ６３．２ｇ（０．３１モル）を加え７０℃で３時間撹拌した。反応液を５０℃まで冷却し、析出した無水フタル酸を濾別した。シクロヘキサン溶液を１，２，４−トリアゾール４２ｇ（０．６１モル）のＴＨＦ２００ｍＬ加熱溶解した液に滴下した。直ちに結晶が析出した。この結晶をろ取し３００ｍＬの水で３回洗い、１００℃で１時間減圧乾燥し３２．０ｇ（通算収率７８％）の１，４−シクロヘキサンジカルボン酸ジトリアゾール異性体混合物を得た。得られた結晶に無水フタル酸が混入していないことをＧＣＭＳで確認した。純度９９．５％（トランス／シス＝１３／８７）
Example 10 (Integrated synthesis from carboxylic acid)
To 25.8 g (0.15 mol) of 1,4-cyclohexanedicarboxylic acid isomer mixture (trans / cis = about 2/8) was added cyclohexane 100 mL, DMF 4 mL, OPC 63.2 g (0.31 mol) at 70 ° C. Stir for hours. The reaction solution was cooled to 50 ° C., and the precipitated phthalic anhydride was filtered off. The cyclohexane solution was added dropwise to a solution obtained by heating and dissolving 42 g (0.61 mol) of 1,2,4-triazole in 200 mL of THF. Crystals immediately precipitated. The crystals were collected by filtration, washed with 300 mL of water three times, and dried under reduced pressure at 100 ° C. for 1 hour to obtain 32.0 g (total yield 78%) of 1,4-cyclohexanedicarboxylic acid ditriazole isomer mixture. It was confirmed by GCMS that phthalic anhydride was not mixed in the obtained crystals. Purity 99.5% (trans / cis = 13/87)
試験例１
ＯＢＢＯＩｍとＯＢＢＯＴｒを０．５ミリモルずつ計り取り、ＮＭＰ４ｍＬに溶解した。それぞれにジエチルアミンを約５．０ミリモル加え、時間毎に反応生成物をＧＣ−ＭＳで追跡した。ＯＢＢＯＩｍとジエチルアミンの反応追跡の結果を図１に示した。１時間後に原料ＯＢＢＯＩｍが９６％残存していた。ＯＢＢＯＩｍが完全に消失するのに２２時間かかった。一方、ＯＢＢＯＴｒとジエチルアミンの反応はわずか１０分で定量的に４，４’−ジフェニルエーテルビス（カルボニルジエチルアミド）に変化した。なお、図１中、Ｅｔ２Ｎ−Ｅｔ２Ｎは４，４’−ジフェニルエーテルビス（カルボニルジエチルアミド）を表し、Ｅｔ２Ｎ−Ｉｍはジフェニルエーテル−４−カルボニルイミダゾールー４’−カルボニルジエチルアミドを表し、Ｉｍ−ＩｍはＯＢＢＯＩｍのモル比を表す。
Test example 1
OBBOIm and OBBOTr were weighed in 0.5 mmol each and dissolved in 4 mL of NMP. About 5.0 mmol of diethylamine was added to each, and the reaction product was monitored by GC-MS every hour. The results of the reaction tracking of OBBOIm and diethylamine are shown in FIG. After 1 hour, 96% of the raw material OBBOIm remained. It took 22 hours for OBBOIm to completely disappear. On the other hand, the reaction between OBBOTr and diethylamine quantitatively changed to 4,4′-diphenyl ether bis ( carbonyldiethylamide ) in only 10 minutes. In FIG. 1, Et2N-Et2N is 4,4'-diphenyl ether represents bis (carbonyl diethylamide), Et2N-Im is diphenyl-4-carbonyl-imidazole - 4 '- represents a carbonyl diethylamide, moles of Im-Im is OBBOIm Represents the ratio.
Claims (2)
It is reacted with di-amine compound or diol compound, be used as a monomer for obtaining a polyamide or polyester, acyl triazole induction of claim 1.
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