JP2014201548A - Method for producing 4,4'-oxybis benzoic acid chloride - Google Patents
Method for producing 4,4'-oxybis benzoic acid chloride Download PDFInfo
- Publication number
- JP2014201548A JP2014201548A JP2013078723A JP2013078723A JP2014201548A JP 2014201548 A JP2014201548 A JP 2014201548A JP 2013078723 A JP2013078723 A JP 2013078723A JP 2013078723 A JP2013078723 A JP 2013078723A JP 2014201548 A JP2014201548 A JP 2014201548A
- Authority
- JP
- Japan
- Prior art keywords
- acid chloride
- reaction
- solvent
- oxybisbenzoic acid
- benzoic 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.)
- Granted
Links
- 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 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 239000012442 inert solvent Substances 0.000 claims abstract description 16
- GXZZHLULZRMUQC-UHFFFAOYSA-N 4-(4-formylphenoxy)benzaldehyde Chemical compound C1=CC(C=O)=CC=C1OC1=CC=C(C=O)C=C1 GXZZHLULZRMUQC-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 10
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 10
- 239000000460 chlorine Substances 0.000 claims abstract description 10
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 239000011737 fluorine Substances 0.000 claims abstract description 5
- QULYNCCPRWKEMF-UHFFFAOYSA-N parachlorobenzotrifluoride Chemical compound FC(F)(F)C1=CC=C(Cl)C=C1 QULYNCCPRWKEMF-UHFFFAOYSA-N 0.000 claims description 8
- XILPLWOGHPSJBK-UHFFFAOYSA-N 1,2-dichloro-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(Cl)C(Cl)=C1 XILPLWOGHPSJBK-UHFFFAOYSA-N 0.000 claims description 3
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 2
- SJBBXFLOLUTGCW-UHFFFAOYSA-N 1,3-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C(F)(F)F)=C1 SJBBXFLOLUTGCW-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 35
- 239000002904 solvent Substances 0.000 abstract description 20
- 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 20
- 239000002994 raw material Substances 0.000 description 15
- 238000004817 gas chromatography Methods 0.000 description 11
- 239000012320 chlorinating reagent Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 230000008034 disappearance Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- QQVDYSUDFZZPSU-UHFFFAOYSA-M chloromethylidene(dimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)=CCl QQVDYSUDFZZPSU-UHFFFAOYSA-M 0.000 description 2
- -1 compound 4,4'-oxybisbenzoic acid chloride Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- DGRVQOKCSKDWIH-UHFFFAOYSA-N 1-chloro-2-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1Cl DGRVQOKCSKDWIH-UHFFFAOYSA-N 0.000 description 1
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 description 1
- LNTGGPJSADTYSG-UHFFFAOYSA-N 2-(2-carbonochloridoylphenoxy)benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1OC1=CC=CC=C1C(Cl)=O LNTGGPJSADTYSG-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- UOQXIWFBQSVDPP-UHFFFAOYSA-N 4-fluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1 UOQXIWFBQSVDPP-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 150000008359 benzonitriles Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、経済性に優れた４，４’−オキシビス安息香酸クロリドの製造方法に関する。 The present invention relates to a method for producing 4,4'-oxybisbenzoic acid chloride excellent in economic efficiency.
４，４’−オキシビス安息香酸クロリドは、高分子材料の原料として有用であり、工業的に安全かつ簡便な製造方法が求められている（特許文献１〜５参照）。 4,4'-Oxybisbenzoic acid chloride is useful as a raw material for polymer materials, and industrially safe and simple production methods are required (see Patent Documents 1 to 5).
４，４’−オキシビス安息香酸をホスゲン、塩化チオニル、五塩化リン、三塩化リン、ビルスマイヤー試薬のような塩素化剤を用いてオキシビス安息香酸クロリドに変換できることは良く知られている。しかし、この反応では高融点で溶解性に乏しい４，４’−オキシビス安息香酸を反応基質とするため、大量の塩素化剤及び／または不活性溶媒が必要となっていた。 It is well known that 4,4'-oxybisbenzoic acid can be converted to oxybisbenzoic acid chloride using chlorinating agents such as phosgene, thionyl chloride, phosphorus pentachloride, phosphorus trichloride, Vilsmeier reagent. However, in this reaction, 4,4'-oxybisbenzoic acid having a high melting point and poor solubility is used as a reaction substrate, so that a large amount of chlorinating agent and / or inert solvent is required.
特許文献１によると、原料４，４’−オキシビス安息香酸に対し塩素化剤である塩化チオニルを８モル倍用い、不活性溶媒である塩化メチレンを３重量倍用いて４，４’−オキシビス安息香酸クロリドを得たと記載されている。原料４，４’−オキシビス安息香酸１モルに対し、使用した塩素化剤と溶媒の容量は、合わせて１１８８ミリリットルに達する。 According to Patent Document 1, the raw material 4,4′-oxybisbenzoic acid is used in an amount of 8 mol times thionyl chloride as a chlorinating agent, and the inert solvent methylene chloride is used 3 times in weight to 4,4′-oxybisbenzoic acid. It is stated that the acid chloride was obtained. The total volume of the chlorinating agent and the solvent used reaches 1188 ml per mole of the raw material 4,4'-oxybisbenzoic acid.
特許文献５によると、原料４，４’−オキシビス安息香酸に対し塩素化剤であるＮ，Ｎ−ジメチルクロロメチレンイミニウムクロリド（ビルスマイヤー試薬）を約２．４モル倍用い、不活性溶媒であるｏ−クロロトルエンを７．２重量倍用いて４，４’−オキシビス安息香酸クロリドを収率７０％で得たと記載されている。原料４，４’−オキシビス安息香酸１モルに対し、使用した溶媒の容量は１７２３ミリリットルに達する。 According to Patent Document 5, N, N-dimethylchloromethylene iminium chloride (Vilsmeier reagent), which is a chlorinating agent, is used in an inert solvent with a chlorinating agent of about 4,4′-oxybisbenzoic acid. It is described that 4,4′-oxybisbenzoic acid chloride was obtained in a yield of 70% using 7.2 weight times of certain o-chlorotoluene. The volume of solvent used reaches 1723 milliliters per mole of raw material 4,4'-oxybisbenzoic acid.
４，４’−オキシビス安息香酸を原料とする上記の従来技術では、高融点で溶解性に乏しい４，４’−オキシビス安息香酸を反応基質とするため大量の塩素化剤及び／または不活性溶媒が必要となる。その結果、単位体積当りの４，４’−オキシビス安息香酸クロリド生産量が少なく、工業的に十分に対応できているとは言えずその改善が望まれる。 In the above prior art using 4,4′-oxybisbenzoic acid as a raw material, a large amount of chlorinating agent and / or inert solvent is used because 4,4′-oxybisbenzoic acid having a high melting point and poor solubility is used as a reaction substrate. Is required. As a result, the amount of 4,4'-oxybisbenzoic acid chloride produced per unit volume is small, and it cannot be said that it is industrially sufficient, and its improvement is desired.
本発明の目的は、４，４’−オキシビス安息香酸クロリドを生産するにあたり、多量の溶媒を使用する必要が無く、生産性の高い製法を提供することである。特に、４，４’−オキシビス安息香酸クロリドの製造における、高い反応収率［α］と、高い体積当たりの生産量（釜効率）［β］とを達成することができる製造方法の提供を目的とする。 An object of the present invention is to provide a production method that does not require the use of a large amount of solvent in producing 4,4'-oxybisbenzoic acid chloride and has high productivity. In particular, an object of the present invention is to provide a production method capable of achieving a high reaction yield [α] and a high production per volume (pot efficiency) [β] in the production of 4,4′-oxybisbenzoic acid chloride. And
本発明者らは、上記の課題解決に向け研究を進めたところ、特に工業的規模での生産を考慮したとき、４，４’−オキシビス安息香酸ではなく、４，４’−オキシビスベンズアルデヒドを原料として用いることが有効であるとの感触を得た。物性面でも、本化合物の融点は６３〜６７℃であり融解しやすく、種々の不活性溶媒に良好に溶解することから、生産性の改善につながる点に着目した。その結果、これを無溶媒溶融状態または塩素に対する不活性溶媒中で塩素化することにより、核塩素化物の副生も殆ど無く、高収率かつ高釜効率で４，４’−オキシビス安息香酸クロリドを生産しうることを見出し、本発明を完成させた。すなわち、上記の課題は下記の手段により解決された。 As a result of researches aimed at solving the above-mentioned problems, the present inventors, in particular, considering 4,4′-oxybisbenzaldehyde instead of 4,4′-oxybisbenzoic acid, considering production on an industrial scale. The feeling that it was effective to use as a raw material was obtained. In terms of physical properties, the compound has a melting point of 63 to 67 ° C. and is easily melted, and is well dissolved in various inert solvents. As a result, by chlorinating this in a solvent-free molten state or in an inert solvent for chlorine, 4,4′-oxybisbenzoic acid chloride is produced in a high yield and high pot efficiency with almost no byproduct of nuclear chlorination. The present invention has been completed. That is, the above problem has been solved by the following means.
〔１〕４，４’−オキシビスベンズアルデヒドと塩素とを反応させることを特徴とする４，４’−オキシビス安息香酸クロリドの製造方法。
〔２〕前記塩素化反応を不活性溶媒中もしくは無溶媒溶融状態で行う〔１〕に記載の製造方法。
〔３〕含フッ素芳香族化合物を前記不活性溶媒として使用する〔２〕に記載の製造方法。
〔４〕前記不活性溶媒がトリフルオロメチルベンゼン、４−クロロトリフルオロメチルベンゼン、１，３−ビストリフルオロメチルベンゼン、３，４−ジクロロトリフルオロメチルベンゼン、またはそれらの組合せである〔２〕または〔３〕に記載の製造方法。
[1] A process for producing 4,4′-oxybisbenzoic acid chloride, which comprises reacting 4,4′-oxybisbenzaldehyde with chlorine.
[2] The production method according to [1], wherein the chlorination reaction is performed in an inert solvent or in a solvent-free molten state.
[3] The production method according to [2], wherein a fluorine-containing aromatic compound is used as the inert solvent.
[4] The inert solvent is trifluoromethylbenzene, 4-chlorotrifluoromethylbenzene, 1,3-bistrifluoromethylbenzene, 3,4-dichlorotrifluoromethylbenzene, or a combination thereof [2] or [3] The production method according to [3].
本発明の製造方法によれば、多量の反応溶媒の使用によらずに、４，４’−オキシビスベンズアルデヒドを塩素と反応させて４，４’−オキシビス安息香酸クロリドを高収率で製造することができる。さらに、本発明の製造方法により、単位体積当りの生産量（釜効率）をも改善させた生産を達成することができる。 According to the production method of the present invention, 4,4′-oxybisbenzaldehyde is reacted with chlorine to produce 4,4′-oxybisbenzoic acid chloride in high yield without using a large amount of reaction solvent. be able to. Furthermore, the production method of the present invention can achieve production with improved production volume per unit volume (pot efficiency).
本発明においては、４，４’−オキシビスベンズアルデヒドを塩素と反応させることにより、４，４’−オキシビス安息香酸クロリドを製造する。以下にその好ましい実施形態について詳細に説明する。 In the present invention, 4,4'-oxybisbenzaldehyde is reacted with chlorine to produce 4,4'-oxybisbenzoic acid chloride. The preferred embodiment will be described in detail below.
前記塩素化の反応温度は５０〜２５０℃の任意の温度で行うことができるが、好ましくは１００〜２００℃である。ただし、無溶媒で行う時は融点以上の温度で行う。 The reaction temperature of the chlorination can be carried out at an arbitrary temperature of 50 to 250 ° C, preferably 100 to 200 ° C. However, when it is carried out without solvent, it is carried out at a temperature higher than the melting point.
塩素は工業的に入手し得るものであればよいが、乾燥されたものが好ましい。４，４’−オキシビスベンズアルデヒドに対する塩素の供給量は化学両論量（２モル倍）であればよいが、反応速度を上げるために、それ以上の塩素を供給することも好ましい。 Chlorine may be industrially available, but is preferably dried. The amount of chlorine supplied to 4,4'-oxybisbenzaldehyde may be a stoichiometric amount (2 mole times), but it is also preferable to supply more chlorine in order to increase the reaction rate.
反応速度を増大させるために、前記の塩素化は、ラジカル開始剤の存在下または光露光下で反応を行うことができる。ラジカル開始剤としては過酸化ベンゾイル、アゾビスイソブチロニトリル等が使用でき、光源としては水銀ランプ、タングステンランプ等が使用できる。 In order to increase the reaction rate, the chlorination can be carried out in the presence of a radical initiator or under light exposure. As the radical initiator, benzoyl peroxide, azobisisobutyronitrile and the like can be used, and as the light source, a mercury lamp, a tungsten lamp and the like can be used.
反応混合物が金属と接触する場合は、金属イオンが副生成物の生成を触媒しないように、金属捕捉剤を反応混合物に添加することが望ましい。金属捕捉剤としては、通常この種の反応に適用されるものを適正量使用すればよい。 When the reaction mixture is in contact with a metal, it is desirable to add a metal scavenger to the reaction mixture so that metal ions do not catalyze the formation of by-products. As the metal scavenger, an appropriate amount usually used for this kind of reaction may be used.
本発明の原料として用いる４，４’−オキシビスベンズアルデヒドは４−フルオロベンズアルデヒドと４−ヒドロキシベンズアルデヒドを縮合させることで得られる（Ｊ．Ｇａｗｒｏｎｓｋｉ， ｅｔ．ａｌ Ｊ．Ｏｒｇ．Ｃｈｅｍ．７０，１０１４７―１０１５０（２００５）。 4,4′-Oxybisbenzaldehyde used as a raw material of the present invention is obtained by condensing 4-fluorobenzaldehyde and 4-hydroxybenzaldehyde (J. Gawronski, et.al J. Org. Chem. 70, 10147-10150). (2005).
本発明の塩素化反応は無溶媒でも行うことができるが、反応に媒体として不活性な溶媒を使用することができる。不活性溶媒としては、ベンゼンに電子吸引性置換基を導入して塩素との反応を抑えることができる、ベンゾニトリル類、含ハロゲン芳香族化合物を使用することが好ましい。反応収率及び環境面、引き続く精製操作を考慮すると、４−クロロトリフルオロメチルベンゼン（ＰＣＢＴＦ）、３，４−ジクロロトリフルオロメチルベンゼン（ＤＣＢＴＦ）、２−クロロトリフルオロメチルベンゼン、１，３−ビストリフルオロメチルベンゼンのような含フッ素芳香族化合物が特に好ましい。特に、精製工程において、ベンゾニトリルに対して、上記の含フッ素芳香族化合物では、生成物の溶解度が高くなりすぎず、良好な再結晶収率が得られるため好ましい。 The chlorination reaction of the present invention can be carried out without a solvent, but an inert solvent can be used as a medium for the reaction. As the inert solvent, it is preferable to use benzonitriles and halogen-containing aromatic compounds that can suppress the reaction with chlorine by introducing an electron-withdrawing substituent into benzene. Considering the reaction yield and environmental aspects, and subsequent purification operations, 4-chlorotrifluoromethylbenzene (PCBTF), 3,4-dichlorotrifluoromethylbenzene (DCBTF), 2-chlorotrifluoromethylbenzene, 1,3- A fluorine-containing aromatic compound such as bistrifluoromethylbenzene is particularly preferred. In particular, in the purification step, the above-described fluorine-containing aromatic compound is preferable with respect to benzonitrile because the solubility of the product does not become too high and a good recrystallization yield is obtained.
ただし、前記塩素化反応には溶媒を使用する必要がなく、一例として挙げると、晶析溶媒を兼ねて使用したとしても、原料４，４’−オキシビスベンズアルデヒド１モルあたり４００ミリリットルで十分に反応が進行する。適正な範囲として示すと、溶媒を使用するときの基質（４，４’−オキシビスベンズアルデヒド）の濃度は、２５質量％以上であることが好ましく、３３質量％以上であることがより好ましい。上限は特にないが、４，４’−オキシビスベンズアルデヒドを単独で用いる無溶媒の場合は実質的に１００質量％となる。このように高濃度ないし無溶媒の反応系で前記塩素化を行うことで、高い単位体積当りの生産量（釜効率）を達成することができる。釜効率は、反応液の総体積（反応溶媒、基質等を含む液体成分の全体積）［Ｖ１］に対する生成した目的化合物（４，４’−オキシビス安息香酸クロリド）の体積［Ｖ２］の比率（β＝Ｖ２／Ｖ２１）で定義できる。釜効率［β］の範囲としては、３０％（体積基準）以上であることが好ましく、５０％（体積基準）以上であることがより好ましい。上限は特にないが、無用媒で高収率で得るときには、ほぼ全量が反応した比率に到達させることができる。 However, it is not necessary to use a solvent for the chlorination reaction. For example, even if it is used as a crystallization solvent, the reaction is sufficiently performed at 400 ml per mole of raw material 4,4′-oxybisbenzaldehyde. Progresses. When shown as an appropriate range, the concentration of the substrate (4,4'-oxybisbenzaldehyde) when the solvent is used is preferably 25% by mass or more, and more preferably 33% by mass or more. Although there is no particular upper limit, in the case of no solvent using 4,4'-oxybisbenzaldehyde alone, it is substantially 100% by mass. Thus, by performing the chlorination in a reaction system having a high concentration or no solvent, a high production volume per unit volume (pot efficiency) can be achieved. The pot efficiency is the ratio of the volume [V2] of the produced target compound (4,4′-oxybisbenzoyl chloride) to the total volume of the reaction liquid (total volume of liquid components including reaction solvent, substrate, etc.) [V1] ( β = V2 / V21). The range of the pot efficiency [β] is preferably 30% (volume basis) or more, and more preferably 50% (volume basis) or more. There is no particular upper limit, but when it is obtained in a high yield with a useless medium, almost the entire amount can be reacted.
本発明の目的化合物４，４’−オキシビス安息香酸クロリドは融点９０℃の固体であり、溶媒から晶析させることで高純度品が得られる。上記の不活性溶媒を使用すれば、この晶析溶媒と上記反応溶媒を兼ねることも可能である。 The target compound 4,4'-oxybisbenzoic acid chloride of the present invention is a solid having a melting point of 90 ° C, and a high purity product can be obtained by crystallization from a solvent. If the above inert solvent is used, the crystallization solvent can also serve as the reaction solvent.
本発明においては、４，４’−オキシビスベンズアルデヒド［仕込み量：Ａ］から、高い収率で目的生成物である４，４’−オキシビス安息香酸クロリド［生成量：Ｂ］を得ることができる。その反応収率［α＝Ｂ／Ａ］は９０％（モル比基準）以上であることが好ましく、９５％（モル比基準）以上であることがより好ましい。本発明によれば、このように高収率で目的化合物である４，４’−オキシビス安息香酸クロリドを得ることができ、その結果、その後の精製の負荷を軽減することができる。 In the present invention, 4,4′-oxybisbenzoic acid chloride [production amount: B], which is the target product, can be obtained in a high yield from 4,4′-oxybisbenzaldehyde [charge amount: A]. . The reaction yield [α = B / A] is preferably 90% (molar ratio basis) or more, and more preferably 95% (molar ratio basis) or more. According to the present invention, the target compound 4,4'-oxybisbenzoic acid chloride can be obtained in such a high yield, and as a result, the subsequent purification load can be reduced.
本発明の製造方法で得られる４，４’−オキシビス安息香酸クロリドは特殊樹脂（高分子材料）の生産原料として使用されている。この原料の供給において、本発明はその製造コストを低減することができ、産業上の利用に資する。特に、塩素化反応の収率が向上することにより工程効率が改善されることはもとより、さらに高釜効率で得られることから製造設備上の制約や負荷も低減することができる。また、本発明によれば、無溶媒とすること、あるいは溶媒種や溶媒量を好適化することにより、引き続く精製工程の負荷を低減したり適性を高めたりすることができ、製造上の改善効果を相乗的に取り込むことができる。 4,4'-Oxybisbenzoic acid chloride obtained by the production method of the present invention is used as a raw material for producing a special resin (polymer material). In the supply of this raw material, the present invention can reduce the manufacturing cost and contribute to industrial use. In particular, the process efficiency is improved by improving the yield of the chlorination reaction, and further, it is possible to reduce the constraints and load on the production equipment because it can be obtained with higher pot efficiency. In addition, according to the present invention, by making no solvent, or by optimizing the solvent type and the amount of solvent, it is possible to reduce the load of the subsequent purification process or to increase the suitability, and to improve the production Can be taken in synergistically.
以下の実施例にて本発明を具体的に説明するが、本発明はこれにより限定して解釈されるものでない。 The present invention will be specifically described with reference to the following examples, but the present invention should not be construed as being limited thereto.
実施例１
攪拌器、温度計及び還流冷却器を備えた３００ミリリットルの４つ口フラスコに、４，４’−オキシビスベンズアルデヒド９０．６ｇ（０．４０ｍｏｌ）、ＰＣＢＴＦ１５８．６ｇを仕込み、加熱攪拌して１４３℃に昇温した。高圧水銀灯を点灯して光照射した。反応温度１４３℃（還流）を保つように、塩素ガス吹込み速度を０．０６モル／時として塩素ガスを供給し反応を開始した。反応開始から１５時間後、ガスクロマトグラフィーにより原料の消失が確認され反応は完結した。これを、ガスクロマトグラフィーを用いて分析したところ４，４’−オキシビス安息香酸クロリドの反応収率は９８．６質量％であった。
上記で得られた反応混合物を約５℃に冷却して４，４’−オキシビス安息香酸クロリドを析出させた。これをヌッチェでろ過し、４−クロロトリフルオロメチルベンゼン５０ｍｌで洗浄後、乾燥させ、４，４’−オキシビス安息香酸クロリドの白色結晶８５．６ｇ（回収率７２．６％）を得た。これを、ガスクロマトグラフィーを用いて分析したころ４，４’−オキシビス安息香酸クロリドの純度は９９．７質量％であった。また、融点は８９．６℃であった。 文献値８８℃；西崎等、工業化学雑誌、７０、１６０７−１６０９、（１９６７）
Example 1
A 300 ml four-necked flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 90.6 g (0.40 mol) of 4,4′-oxybisbenzaldehyde and 158.6 g of PCBTF, and heated and stirred to 143 ° C. The temperature was raised to. A high pressure mercury lamp was turned on and irradiated with light. The reaction was started by supplying chlorine gas at a chlorine gas blowing rate of 0.06 mol / hour so as to maintain a reaction temperature of 143 ° C. (reflux). After 15 hours from the start of the reaction, disappearance of the raw materials was confirmed by gas chromatography, and the reaction was completed. When this was analyzed using gas chromatography, the reaction yield of 4,4′-oxybisbenzoic acid chloride was 98.6% by mass.
The reaction mixture obtained above was cooled to about 5 ° C. to precipitate 4,4′-oxybisbenzoic acid chloride. This was filtered with Nutsche, washed with 50 ml of 4-chlorotrifluoromethylbenzene, and dried to obtain 85.6 g of 4,4′-oxybisbenzoic acid chloride as a white crystal (recovery rate 72.6%). When this was analyzed using gas chromatography, the purity of 4,4′-oxybisbenzoic acid chloride was 99.7% by mass. The melting point was 89.6 ° C. Literature value 88 ° C; Nishizaki et al., Industrial Chemical Journal, 70, 1607-1609, (1967)
実施例２
光照射を行わず遮光条件下で行なったこと以外は実施例１と同じ条件で４，４’−オキシビス安息香酸クロリドを製造した。反応開始から２０時間後、ガスクロマトグラフィーにより原料の消失が確認され反応は完結した。これを、ガスクロマトグラフィーを用いて分析したころ４，４’−オキシビス安息香酸クロリドの反応収率は９８．４質量％であった。
Example 2
4,4′-Oxybisbenzoic acid chloride was produced under the same conditions as in Example 1 except that light irradiation was not performed and light-shielding conditions were used. After 20 hours from the start of the reaction, disappearance of the raw materials was confirmed by gas chromatography, and the reaction was completed. When this was analyzed using gas chromatography, the reaction yield of 4,4′-oxybisbenzoic acid chloride was 98.4% by mass.
実施例３
溶媒にＰＣＢＴＦを使用せずに行なったこと以外は実施例１と同じ条件で４，４’−オキシビス安息香酸クロリドを製造した。反応開始から２０時間後、ガスクロマトグラフィーにより原料の消失が確認され反応は完結した。これを、ガスクロマトグラフィーを用いて分析したころ４，４’−オキシビス安息香酸クロリドの反応収率は９６．１質量％であった。
Example 3
4,4′-Oxybisbenzoic acid chloride was produced under the same conditions as in Example 1 except that it was carried out without using PCBTF as a solvent. After 20 hours from the start of the reaction, disappearance of the raw materials was confirmed by gas chromatography, and the reaction was completed. When this was analyzed using gas chromatography, the reaction yield of 4,4′-oxybisbenzoic acid chloride was 96.1% by mass.
実施例４
溶媒ＰＣＢＴＦを７２．５ｇ使用したこと以外は実施例１と同じ条件で４，４’−オキシビス安息香酸クロリドを製造した。反応開始から１８時間後、ガスクロマトグラフィーにより原料の消失が確認され反応は完結した。これを、ガスクロマトグラフィーを用いて分析したころ４，４’−オキシビス安息香酸クロリドの反応収率は９８．１質量％であった。
Example 4
4,4′-Oxybisbenzoic acid chloride was produced under the same conditions as in Example 1 except that 72.5 g of the solvent PCBTF was used. After 18 hours from the start of the reaction, the disappearance of the raw materials was confirmed by gas chromatography, and the reaction was completed. When this was analyzed using gas chromatography, the reaction yield of 4,4′-oxybisbenzoic acid chloride was 98.1% by mass.
実施例５
溶媒ＤＣＢＴＦを１５８．６ｇ使用し、反応温度を１７５℃（還流）としたこと以外は実施例１と同じ条件で４，４’−オキシビス安息香酸クロリドを製造した。反応開始から１２時間後、ガスクロマトグラフィーにより原料の消失が確認され反応は完結した。これを、ガスクロマトグラフィーを用いて分析したころ４，４’−オキシビス安息香酸クロリドの反応収率は９８．３質量％であった。
Example 5
4,4′-Oxybisbenzoic acid chloride was produced under the same conditions as in Example 1 except that 158.6 g of the solvent DCBTF was used and the reaction temperature was 175 ° C. (reflux). After 12 hours from the start of the reaction, the disappearance of the raw materials was confirmed by gas chromatography, and the reaction was completed. When this was analyzed using gas chromatography, the reaction yield of 4,4′-oxybisbenzoic acid chloride was 98.3% by mass.
実施例１〜５、特許文献１および特許文献５の反応収率、釜効率を表１にまとめた。
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013078723A JP6126440B2 (en) | 2013-04-04 | 2013-04-04 | Method for producing 4,4'-oxybisbenzoic acid chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013078723A JP6126440B2 (en) | 2013-04-04 | 2013-04-04 | Method for producing 4,4'-oxybisbenzoic acid chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2014201548A true JP2014201548A (en) | 2014-10-27 |
| JP6126440B2 JP6126440B2 (en) | 2017-05-10 |
Family
ID=52352315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013078723A Active JP6126440B2 (en) | 2013-04-04 | 2013-04-04 | Method for producing 4,4'-oxybisbenzoic acid chloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6126440B2 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05320093A (en) * | 1991-04-30 | 1993-12-03 | Ihara Chem Ind Co Ltd | Production of biphenyldicarboxylic acid dichloride |
| JPH10182547A (en) * | 1996-12-20 | 1998-07-07 | Mitsubishi Gas Chem Co Inc | Production of benzoyl chloride compounds |
| JPH11236346A (en) * | 1997-12-12 | 1999-08-31 | Clariant Gmbh | Production of 3-chloro-4-fluorobenzoyl chloride |
| JP2000281637A (en) * | 1999-03-29 | 2000-10-10 | Showa Denko Kk | Production of cyanobenzoyl halide |
| JP2012136502A (en) * | 2010-12-10 | 2012-07-19 | Ihara Nikkei Kagaku Kogyo Kk | Method for producing imidoyl chloride compound, and method for producing various compounds by using the same |
-
2013
- 2013-04-04 JP JP2013078723A patent/JP6126440B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05320093A (en) * | 1991-04-30 | 1993-12-03 | Ihara Chem Ind Co Ltd | Production of biphenyldicarboxylic acid dichloride |
| JPH10182547A (en) * | 1996-12-20 | 1998-07-07 | Mitsubishi Gas Chem Co Inc | Production of benzoyl chloride compounds |
| JPH11236346A (en) * | 1997-12-12 | 1999-08-31 | Clariant Gmbh | Production of 3-chloro-4-fluorobenzoyl chloride |
| JP2000281637A (en) * | 1999-03-29 | 2000-10-10 | Showa Denko Kk | Production of cyanobenzoyl halide |
| JP2012136502A (en) * | 2010-12-10 | 2012-07-19 | Ihara Nikkei Kagaku Kogyo Kk | Method for producing imidoyl chloride compound, and method for producing various compounds by using the same |
Non-Patent Citations (1)
| Title |
|---|
| CLARKE, H.T. ET AL.: "o-Chlorobenzoyl chloride", ORGANIC SYNTHESIS, vol. 1, JPN6016029712, 1941, pages 155, ISSN: 0003373067 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6126440B2 (en) | 2017-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106458841B (en) | Method for producing 2-halogen-acrylates | |
| JPWO2019208807A1 (en) | Method for producing aromatic nitrile compound | |
| JP4923184B2 (en) | Method for producing chloroethylene carbonate | |
| JP6126440B2 (en) | Method for producing 4,4'-oxybisbenzoic acid chloride | |
| JP2017214364A (en) | Method for producing alcohols having fluorene skeleton | |
| JP3918883B2 (en) | Method for producing benzoyl chlorides | |
| KR101923036B1 (en) | Preparation of phthaloyl chloride | |
| JP2017171620A (en) | Manufacturing method of acetamide derivative | |
| JP6902275B2 (en) | Method for Producing Aromatic Complex Polycyclic Halogen Compound | |
| JP5795519B2 (en) | Method for producing chlorosulfonylbenzoyl chloride compound | |
| Pan et al. | A new protocol for the synthesis of 4, 7, 12, 15-tetrachloro [2.2] paracyclophane | |
| JP5188475B2 (en) | Process for producing 2- (3-nitrobenzylidene) isopropyl acetoacetate | |
| JP3874925B2 (en) | Method for producing chloromethylphenylacetic acid | |
| JP2019131487A (en) | Triaryltriazine compound, and manufacturing method therefor | |
| JP2018062513A (en) | Method for producing sulfonamide compound | |
| JP6915189B1 (en) | High-purity 2-naphthylacetonitrile and its production method | |
| JP5250199B2 (en) | Method for producing trichloromethanesulfonyl chloride | |
| JP6678986B2 (en) | Method for producing α-bromo-α-fluorocarboxylic acid esters | |
| JP2006206469A (en) | 3-oxo-propionic acid ester and method for producing 1,2-diarylethanone using the same | |
| JP2013245193A (en) | Method for producing chlorinated fluorene compound | |
| JP2549890B2 (en) | Process for producing bis (trichloromethyl) diphenyl ether | |
| CN106414414A (en) | Method for manufacturing triketone compound | |
| JP2021185157A (en) | Alkylation of picolinamide using substituted chloroacylal utilizing crown ether catalyst | |
| JP5649288B2 (en) | Method for producing phthalic dichloride compound and catalyst used in the production method | |
| JP4374975B2 (en) | Method for producing allyl-substituted aryl compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160225 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20160713 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160809 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20161007 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20170314 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20170407 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6126440 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |