JPH07118195A - 2-ethylanthraquinone and its production - Google Patents
2-ethylanthraquinone and its productionInfo
- Publication number
- JPH07118195A JPH07118195A JP29129593A JP29129593A JPH07118195A JP H07118195 A JPH07118195 A JP H07118195A JP 29129593 A JP29129593 A JP 29129593A JP 29129593 A JP29129593 A JP 29129593A JP H07118195 A JPH07118195 A JP H07118195A
- Authority
- JP
- Japan
- Prior art keywords
- ethylanthraquinone
- ethylbenzoyl
- benzoic acid
- parts
- ethylbenzene
- 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.)
- Pending
Links
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title claims description 37
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 92
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 56
- JZFDKGFWNSQAHU-UHFFFAOYSA-N 2-(4-ethylbenzoyl)benzoic acid Chemical compound C1=CC(CC)=CC=C1C(=O)C1=CC=CC=C1C(O)=O JZFDKGFWNSQAHU-UHFFFAOYSA-N 0.000 claims abstract description 44
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 23
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000460 chlorine Substances 0.000 claims abstract description 12
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims abstract description 8
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000004056 anthraquinones Chemical class 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 21
- 150000001805 chlorine compounds Chemical class 0.000 claims description 19
- -1 2-Ethyl Chemical group 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000007363 ring formation reaction Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000003505 polymerization initiator Substances 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000013043 chemical agent Substances 0.000 abstract 1
- 239000000975 dye Substances 0.000 abstract 1
- 239000000976 ink Substances 0.000 abstract 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000002844 melting Methods 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000011084 recovery Methods 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- HSKPJQYAHCKJQC-UHFFFAOYSA-N 1-ethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CC HSKPJQYAHCKJQC-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- HYJODZUSLXOFNC-UHFFFAOYSA-N [S].[Cl] Chemical compound [S].[Cl] HYJODZUSLXOFNC-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 5
- 239000005711 Benzoic acid Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N (2-methylphenyl)methanol Chemical compound CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 description 1
- YWECCEXWKFHHQJ-UHFFFAOYSA-N 2-(4-chlorobenzoyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=C(Cl)C=C1 YWECCEXWKFHHQJ-UHFFFAOYSA-N 0.000 description 1
- ICQOWIXIHDDXDI-UHFFFAOYSA-N 2-(4-methylbenzoyl)benzoic acid Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1C(O)=O ICQOWIXIHDDXDI-UHFFFAOYSA-N 0.000 description 1
- HXQPUEQDBSPXTE-UHFFFAOYSA-N Diisobutylcarbinol Chemical compound CC(C)CC(O)CC(C)C HXQPUEQDBSPXTE-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006210 cyclodehydration reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、塩素化合物を含有しな
い２−エチルアントラキノンに関する。更に詳細には、
染料中間体、紫外線硬化樹脂あるいはＵＶインキの重合
開始剤、あるいはアントラキノン法過酸化水素製造に使
用される２−エチルアントラキノンに関する。FIELD OF THE INVENTION The present invention relates to 2-ethylanthraquinone containing no chlorine compound. More specifically,
The present invention relates to a dye intermediate, a polymerization initiator for an ultraviolet curable resin or a UV ink, or 2-ethylanthraquinone used for hydrogen peroxide production by the anthraquinone method.
【０００２】[0002]
【従来の技術】２−エチルアントラキノンは紫外線硬化
樹脂あるいはＵＶインキの重合開始剤等に用いられてい
る。このような紫外線硬化樹脂等を金属、半導体等の材
料に使用する場合、従来の塩素化合物を含有する２−エ
チルアントラキノンを使用して製造されたものでは材料
が腐食される場合がある。また、これらの材料の廃棄、
焼却における環境面への影響等からもこれらに使用する
２−エチルアントラキノンは出来るだけ塩素化合物の混
入のないものが望まれている。2. Description of the Related Art 2-Ethylanthraquinone is used as an ultraviolet curable resin or a polymerization initiator for UV ink. When such an ultraviolet curable resin or the like is used for a material such as a metal or a semiconductor, a material produced using 2-ethylanthraquinone containing a conventional chlorine compound may be corroded. Also, the disposal of these materials,
In view of the environmental impact of incineration, it is desired that 2-ethylanthraquinone used for these should be as free of chlorine compounds as possible.
【０００３】また、２−エチルアントラキノンはアント
ラキノン法過酸化水素製造における重要な媒体である。
この場合、２−エチルアントラキノンは溶剤中、パラジ
ウムや白金等の金属触媒の存在下に水素で還元され、次
に酸素あるいは空気で酸化され過酸化水素を発生して元
の２−エチルアントラキノンに再生される。この工程は
連続的に循環しておこなわれ、２−エチルアントラキノ
ンは繰り返し使用されるが、水素還元において使用され
ている高価な金属触媒の劣化を防ぐため、あるいは使用
される装置や機器の腐食を防ぐため、これに用いられる
２−エチルアントラキノンは出来るだけ塩素化合物を含
有しないものが望まれている。Further, 2-ethylanthraquinone is an important medium in the anthraquinone method hydrogen peroxide production.
In this case, 2-ethylanthraquinone is reduced with hydrogen in the presence of a metal catalyst such as palladium or platinum in a solvent, then oxidized with oxygen or air to generate hydrogen peroxide, and regenerated to the original 2-ethylanthraquinone. To be done. This process is continuously circulated, and 2-ethylanthraquinone is used repeatedly, but to prevent the deterioration of expensive metal catalysts used in hydrogen reduction or to corrode the equipment and devices used. In order to prevent this, 2-ethylanthraquinone used for this purpose is desired to contain as little chlorine compounds as possible.
【０００４】現在２−エチルアントラキノンは、反応操
作の容易さ、製造コスト面の有利性等の理由で、例えば
ＰＢ−４４９６１等に記載されているように、下記の反
応式に示されるプロセスで製造されている。At present, 2-ethylanthraquinone is produced by the process represented by the following reaction formula as described in, for example, PB-44961 because of the ease of reaction operation and the advantage of production cost. Has been done.
【０００５】[0005]
【化１】 先ず、反応式（１）に示されるように、エチルベンゼン
と無水フタル酸とを塩化アルミニウムの存在下にクロル
ベンゼンを溶媒として用いて反応させ、中間体である２
−（４−エチルベンゾイル）安息香酸を製造する。次に
反応式（２）に示されるように、この２−（４−エチル
ベンゾイル）安息香酸を発煙硫酸中で脱水環化して２−
エチルアントラキノンを製造する。[Chemical 1] First, as shown in reaction formula (1), ethylbenzene and phthalic anhydride are reacted in the presence of aluminum chloride using chlorobenzene as a solvent to give an intermediate 2
-(4-Ethylbenzoyl) benzoic acid is prepared. Next, as shown in reaction formula (2), this 2- (4-ethylbenzoyl) benzoic acid is dehydrated and cyclized in fuming sulfuric acid to give 2-
Produces ethylanthraquinone.
【０００６】しかしながら、この製造方法で製造される
２−エチルアントラキノンは、少量の塩素化合物の混入
が不可避であり、精製操作によっても完全に除くことは
困難であった。However, 2-ethylanthraquinone produced by this production method inevitably contains a small amount of chlorine compounds, and it is difficult to completely remove it even by a refining operation.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、塩素化合物
の混入のない２−エチルアントラキノン及びその製造方
法を得ようとするものである。DISCLOSURE OF THE INVENTION The present invention is intended to obtain 2-ethylanthraquinone and a method for producing the same, which is free of chlorine compounds.
【０００８】[0008]
【課題を解決するための手段】本発明者等は、前記した
問題点を解決すべく鋭意検討した結果、特定の反応条件
を用いることによって塩素化合物を含まない２−エチル
アントラキノンを製造できる事を見いだし本発明を完成
した。Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have found that 2-ethylanthraquinone containing no chlorine compound can be produced by using specific reaction conditions. Found and completed the present invention.
【０００９】即ち、本発明は、実質的に塩素化合物を含
有しない２−エチルアントラキノンに関する。That is, the present invention relates to 2-ethylanthraquinone substantially free of chlorine compounds.
【００１０】本発明はまた、エチルベンゼンと無水フタ
ル酸のみから塩化アルミニウムの存在下に２−（４−エ
チルベンゼン）安息香酸を製造し、次いでこの２−（４
−エチルベンゾイル）安息香酸を環化する、実質的に塩
素化合物を含まない２−エチルアントラキノンの製造方
法に関する。The present invention also produces 2- (4-ethylbenzene) benzoic acid in the presence of aluminum chloride from ethylbenzene and phthalic anhydride alone, and then the 2- (4
-Ethylbenzoyl) benzoic acid cyclizing method for producing 2-ethylanthraquinone substantially free of chlorine compounds.
【００１１】本発明の、実質的に塩素化合物を含有しな
い２−エチルアントラキノンは、塩素硫黄分析装置ＴＳ
Ｘ−１０型（三菱化成工業株式会社製）による塩素分の
測定（検出限界０．１ｐｐｍ）で、塩素分が検出されな
い。The 2-ethylanthraquinone containing substantially no chlorine compound of the present invention is a chlorine-sulfur analyzer TS.
Chlorine content is not detected by measurement of chlorine content with X-10 type (manufactured by Mitsubishi Kasei Co., Ltd.) (detection limit 0.1 ppm).
【００１２】本発明の２−エチルアントラキノンは、以
下のような製造方法により製造される。The 2-ethylanthraquinone of the present invention is produced by the following production method.
【００１３】まず第１工程で、エチルベンゼンと無水フ
タル酸を撹拌分散し、これに塩化アルミニウムを添加、
反応して２−（４−エチルベンゾイル）安息香酸を製造
する。First, in the first step, ethylbenzene and phthalic anhydride are stirred and dispersed, and aluminum chloride is added thereto.
Reacting produces 2- (4-ethylbenzoyl) benzoic acid.
【００１４】この第１工程において、エチルベンゼンの
使用量は無水フタル酸１重量部に対して５〜２０重量
部、より好ましくは８〜１５重量部である。エチルベン
ゼンの使用量が無水フタル酸の使用重量の５倍重量部よ
り少ないと、反応物の溶解不良及び粘度上昇のため反応
が不均一となり、２−（４−エチルベンゾイル）安息香
酸の収率及び純度が低下する。２０倍重量部より多い場
合は、２−（４−エチルベンゾイル）安息香酸の純度に
は影響しないが収率が低下する傾向にあり、また過剰分
のエチルベンゼンの回収率が低下する。In the first step, the amount of ethylbenzene used is 5 to 20 parts by weight, more preferably 8 to 15 parts by weight, based on 1 part by weight of phthalic anhydride. When the amount of ethylbenzene used is less than 5 parts by weight of the amount of phthalic anhydride used, the reaction becomes inhomogeneous due to poor dissolution of the reaction product and increase in viscosity, and the yield of 2- (4-ethylbenzoyl) benzoic acid and Purity decreases. When it is more than 20 times by weight, the yield of 2- (4-ethylbenzoyl) benzoic acid is not affected but the yield tends to decrease, and the recovery rate of excess ethylbenzene decreases.
【００１５】使用するエチルベンゼンは含水率５００ｐ
ｐｍ以下であることが好ましい。エチルベンゼンの含水
率が５００ｐｐｍより大きいと、反応物が難溶性の塊状
物を形成し、撹拌が不能になる場合があり、２−（４−
エチルベンゾイル）安息香酸の収率、品質が低下する。The ethylbenzene used has a water content of 500 p.
It is preferably pm or less. If the water content of ethylbenzene is more than 500 ppm, the reaction product may form a sparingly soluble lump, and stirring may be impossible.
The yield and quality of ethylbenzoyl) benzoic acid decrease.
【００１６】エチルベンゼンの含水率が５００ｐｐｍよ
り大きい場合、蒸留精製、シリカゲル等による脱水等の
処理により５００ｐｐｍ以下にして使用することができ
る。When the water content of ethylbenzene is more than 500 ppm, it can be used by adjusting it to 500 ppm or less by treatment such as distillation purification and dehydration with silica gel.
【００１７】塩化アルミニウムの使用量は無水フタル酸
１重量部に対して１．７〜２．０重量部（無水フタル酸
の１．９〜２．２倍モル）である。塩化アルミニウムの
使用量が無水フタル酸の１．７倍重量部より少ないと２
−（４−エチルベンゾイル）安息香酸の収率が低下す
る。また２．０倍重量部より多いと２−（４−エチルベ
ンゾイル）安息香酸の純度が低下し、塩素化合物混入の
一因ともなり得る。The amount of aluminum chloride used is 1.7 to 2.0 parts by weight (1.9 to 2.2 times the molar amount of phthalic anhydride) per 1 part by weight of phthalic anhydride. 2 if the amount of aluminum chloride used is less than 1.7 parts by weight of phthalic anhydride
The yield of-(4-ethylbenzoyl) benzoic acid decreases. On the other hand, if it is more than 2.0 parts by weight, the purity of 2- (4-ethylbenzoyl) benzoic acid is lowered, which may be a cause of mixing of chlorine compounds.
【００１８】エチルベンゼンと無水フタル酸の分散液に
塩化アルミニウムを添加する温度、及びその後の反応温
度は０〜４０℃が好ましく、５〜３０℃が特に好まし
い。０℃より低いと反応物の溶解度の低下により撹拌が
不十分となるため、大過剰のエチルベンゼンを使用する
ことが必要であり、４０℃より高いと２−（４−エチル
ベンゼン）安息香酸の純度が低下する。The temperature at which aluminum chloride is added to the dispersion of ethylbenzene and phthalic anhydride, and the reaction temperature thereafter is preferably 0 to 40 ° C, particularly preferably 5 to 30 ° C. When the temperature is lower than 0 ° C, the solubility of the reaction product is lowered and the stirring becomes insufficient. Therefore, it is necessary to use a large excess of ethylbenzene, and when the temperature is higher than 40 ° C, the purity of 2- (4-ethylbenzene) benzoic acid is high. descend.
【００１９】塩化アルミニウムの添加に要する時間は反
応スケールによって異なるが、前記した温度を保つよう
徐々に添加するのが好ましい。The time required for the addition of aluminum chloride varies depending on the reaction scale, but it is preferable to add it gradually so as to maintain the above temperature.
【００２０】反応時間は塩化アルミニウムを全量添加完
了してから２０分〜４時間が好ましく、３０分〜２時間
が特に好ましい。２０分より短いと２−（４−エチルベ
ンゾイル）安息香酸の収率が低下する傾向があり、４時
間より長いと２−（４−エチルベンゾイル）安息香酸の
純度及び過剰エチルベンゼンの回収物の純度が低下す
る。The reaction time is preferably 20 minutes to 4 hours, and particularly preferably 30 minutes to 2 hours after the addition of all the aluminum chloride is completed. If it is shorter than 20 minutes, the yield of 2- (4-ethylbenzoyl) benzoic acid tends to decrease, and if it is longer than 4 hours, the purity of 2- (4-ethylbenzoyl) benzoic acid and the purity of the recovered product of excess ethylbenzene are high. Is reduced.
【００２１】本反応工程はクロルベンゼン等の反応溶媒
を併用しないことが特徴の一つであるが、本発明の主旨
に影響を及ぼさない非塩素系不活性溶媒を併用すること
は可能である。One of the characteristics of this reaction step is that a reaction solvent such as chlorobenzene is not used in combination, but it is possible to use a non-chlorine inert solvent that does not affect the gist of the present invention.
【００２２】反応終了後、反応液を希硫酸に排出し、加
温して塩化アルミニウムとの錯体を分解する。目的物で
ある２−（４−エチルベンゾイル）安息香酸は過剰に使
用したエチルベンゼンの残分に抽出されるが、この際必
要に応じてさらにエチルベンゼンを追加しても良い。エ
チルベンゼン抽出液を分取し、湯洗する。After the reaction is completed, the reaction solution is discharged into diluted sulfuric acid and heated to decompose the complex with aluminum chloride. The desired product, 2- (4-ethylbenzoyl) benzoic acid, is extracted in the residue of the ethylbenzene used in excess. At this time, ethylbenzene may be added if necessary. Separate the ethylbenzene extract and wash with hot water.
【００２３】エチルベンゼン抽出液からエチルベンゼン
を濃縮除去することにより２−（４−エチルベンゾイ
ル）安息香酸が得られる。この２−（４−エチルベンゾ
イル）安息香酸は本発明の２−エチルアントラキノンを
製造するための中間体としてこのままでも十分使用可能
であるが、塩素化合物以外の不純物についてさらに高純
度である２−エチルアントラキノンを得るために、エチ
ルベンゼン抽出液から２−（４−エチルベンゾイル）安
息香酸をアルカリ水溶液に再抽出し、希硫酸や希塩酸等
で酸析し、濾取水洗乾燥して得ることも良い。2- (4-Ethylbenzoyl) benzoic acid can be obtained by concentrating and removing ethylbenzene from the ethylbenzene extract. This 2- (4-ethylbenzoyl) benzoic acid can be sufficiently used as it is as an intermediate for producing 2-ethylanthraquinone of the present invention, but 2-ethyl having a higher purity with respect to impurities other than chlorine compounds. To obtain anthraquinone, 2- (4-ethylbenzoyl) benzoic acid may be reextracted from an ethylbenzene extract into an aqueous alkaline solution, acidified with diluted sulfuric acid or diluted hydrochloric acid, filtered, washed with water and dried.
【００２４】第１工程で製造した２−（４−エチルベン
ゾイル）安息香酸を、第２工程で環化して２−エチルア
ントラキノンを製造する。The 2- (4-ethylbenzoyl) benzoic acid produced in the first step is cyclized in the second step to produce 2-ethylanthraquinone.
【００２５】この第２工程は通常、２−（４−エチルベ
ンゾイル）安息香酸を発煙硫酸、活性白土、超強酸性化
合物等の存在下に脱水環化することにより達成される。
特に、発煙硫酸の存在下に加熱する方法によるのが好ま
しい。The second step is usually accomplished by subjecting 2- (4-ethylbenzoyl) benzoic acid to cyclodehydration in the presence of fuming sulfuric acid, activated clay, ultra-strong acidic compound and the like.
In particular, the method of heating in the presence of fuming sulfuric acid is preferable.
【００２６】使用する発煙硫酸の濃度は２〜３０％、好
ましくは５〜２５％である。発煙硫酸の使用量は、使用
する２−（４−エチルベンゾイル）安息香酸１重量部に
対し２〜１０重量部、好ましくは４〜６重量部である。
反応時間は０．５〜１０時間、好ましくは１〜３時間で
ある。反応温度は７０〜１１０℃、好ましくは８０〜１
１０℃である。The concentration of fuming sulfuric acid used is 2 to 30%, preferably 5 to 25%. The amount of fuming sulfuric acid used is 2 to 10 parts by weight, preferably 4 to 6 parts by weight, relative to 1 part by weight of 2- (4-ethylbenzoyl) benzoic acid used.
The reaction time is 0.5 to 10 hours, preferably 1 to 3 hours. The reaction temperature is 70 to 110 ° C, preferably 80 to 1
It is 10 ° C.
【００２７】反応終了後、反応液を冷却、水に排出する
と２−エチルアントラキノンが沈殿として得られる。沈
殿を濾取、水洗、希アルカリ洗、水洗、乾燥して得られ
た製品、あるいは沈殿を有機溶剤で抽出し、抽出液を湯
洗、希アルカリ洗、湯洗、濃縮して得られた製品はこの
ままでも十分高純度であり塩素化合物を含有しないが、
塩素化合物以外の混入物についてよりいっそうの高純度
を求めるなら、更に蒸留による精製、あるいはトルエン
−メタノール混合溶媒等の有機溶媒を用いた再結晶等の
精製を行っても良い。After completion of the reaction, the reaction solution is cooled and discharged into water to obtain 2-ethylanthraquinone as a precipitate. A product obtained by filtering the precipitate, washing with water, washing with a dilute alkali, washing with water, and drying, or a product obtained by extracting the precipitate with an organic solvent and washing the extract with hot water, washing with a dilute alkali, washing with water, and concentration. Is pure enough and does not contain chlorine compounds,
If higher purity is required for contaminants other than chlorine compounds, purification by distillation or purification such as recrystallization using an organic solvent such as a toluene-methanol mixed solvent may be performed.
【００２８】前述したごとく、従来の２−エチルアント
ラキノンの製造方法においては、中間体である２−（４
−エチルベンゾイル）安息香酸を製造する際に溶媒とし
てクロルベンゼンを使用している。As described above, in the conventional method for producing 2-ethylanthraquinone, 2- (4) which is an intermediate is used.
Chlorobenzene is used as a solvent in the production of -ethylbenzoyl) benzoic acid.
【００２９】本発明者等は、２−エチルアントラキノン
に含まれる塩素化合物に対して詳細な研究を行なった結
果、塩素化合物のかなりの部分が溶媒として使用したク
ロルベンゼンに由来することを発見した。そこで当然、
中間体である２−（４−エチルベンゾイル）安息香酸の
製造において、クロルベンゼンを使用せず、他の溶媒を
使用する事、あるいは原料であるエチルベンゼンを過剰
使用して溶媒として兼用する事が考えられるが、これら
の試みは２−エチルアントラキノンの製造に於いて直ち
には十分満足いく結果を与えなかった。As a result of detailed research on the chlorine compound contained in 2-ethylanthraquinone, the present inventors have found that a considerable part of the chlorine compound is derived from chlorobenzene used as a solvent. So, of course,
In the production of 2- (4-ethylbenzoyl) benzoic acid, which is an intermediate, it is possible to use another solvent without using chlorobenzene, or to use ethylbenzene as a raw material in excess and also use it as a solvent. However, these attempts did not immediately give satisfactory results in the production of 2-ethylanthraquinone.
【００３０】即ち、他の溶媒の使用において、この種の
反応で使用され得る溶媒、例えば二硫化炭素、塩化メチ
レン、ニトロメタンあるいはニトロベンゼン等は、いず
れも人、環境に対して強い毒性を有している。また、特
に二硫化炭素や塩化メチレン等の脂肪族塩素化合物は、
沸点が低く、蒸気圧が高いため製造作業上取り扱いが難
しい。また、ニトロメタン、ニトロベンゼン等のニトロ
系の溶剤は、２−（４−エチルベンゾイル）安息香酸の
反応収率が低い。That is, when other solvents are used, any solvent which can be used in this kind of reaction, such as carbon disulfide, methylene chloride, nitromethane or nitrobenzene, has a strong toxicity to humans and the environment. There is. Also, especially aliphatic chlorine compounds such as carbon disulfide and methylene chloride,
Low boiling point and high vapor pressure make it difficult to handle during manufacturing. In addition, nitro solvents such as nitromethane and nitrobenzene have a low reaction yield of 2- (4-ethylbenzoyl) benzoic acid.
【００３１】一方、原料であるエチルベンゼン等のベン
ゼン誘導体を溶媒を兼ねて大過剰に使用する方法は、例
えば、ＦＩＡＴ１３１３等に、トルエンと無水フタル酸
より２−（４−メチルベンゾイル安息香酸を製造する方
法や、クロルベンゼンと無水フタル酸より２−（４−ク
ロルベンゾイル）安息香酸を製造する方法が開示されて
いる。しかしながら、２−（４−エチルベンゾイル）安
息香酸の製造においては、反応条件によってはエチルベ
ンゼンが塩化アルミニウムにより変質し易く、この副生
物が無水フタル酸と反応することによって、２−（４−
エチルベンゾイル）安息香酸の収量低下、品質低下が生
じる。また、エチルベンゼンの変質は、過剰分のエチル
ベンゼンの回収率の低下、品質の低下をもたらす。更
に、エチルベンゼンの変質は反応物の溶解度の低下をも
たらし、時には反応物と反応原料とからなる塊状物質を
生成して、撹拌ができなくなる等のトラブルの原因とな
る。On the other hand, the method of using a benzene derivative such as ethylbenzene as a raw material in a large excess also as a solvent is, for example, FIAT 1313 to produce 2- (4-methylbenzoylbenzoic acid) from toluene and phthalic anhydride. However, a method for producing 2- (4-chlorobenzoyl) benzoic acid from chlorobenzene and phthalic anhydride is disclosed, however, in the production of 2- (4-ethylbenzoyl) benzoic acid, depending on the reaction conditions. Ethylbenzene is easily altered by aluminum chloride, and this by-product reacts with phthalic anhydride to give 2- (4-
The yield and quality of ethylbenzoyl) benzoic acid decrease. Further, the alteration of ethylbenzene causes a reduction in recovery rate of excess ethylbenzene and a reduction in quality. Further, the deterioration of ethylbenzene causes a decrease in the solubility of the reaction product, and sometimes a lump substance composed of the reaction product and the reaction raw material is produced, which causes troubles such as the inability to stir.
【００３２】本発明者等は塩素化合物を含有しない２−
エチルアントラキノンの製造を鋭意検討した結果、エチ
ルベンゼンを溶媒を兼ねて過剰使用し、かつ前記した欠
点を解決して目的物を製造する方法を見出したものであ
る。The present inventors have found that 2-
As a result of intensive studies on the production of ethylanthraquinone, the inventors have found a method for producing an intended product by using ethylbenzene in excess as a solvent and solving the above-mentioned drawbacks.
【００３３】[0033]
【実施例】以下に、本発明を実施例によりさらに詳細に
説明するが、本発明はこれらの実施例により限定される
ものでない。実施例中、部は重量部を示し、％はモル％
を示す。The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples, "part" means "part by weight" and "%" means "mol%"
Indicates.
【００３４】［実施例１］ ２−エチルアントラキノン
の製造 （１）２−（４−エチルベンゾイル）安息香酸の製造 含水率４００ｐｐｍのエチルベンゼン４３３部に無水フ
タル酸４５部を加え、１５〜２０℃で撹拌分散した。こ
れに冷却下塩化アルミニウム８１部を少量づつ同温を保
って添加した。塩化アルミニウムを全量添加するのに約
２時間を要した。全量添加後、更に２０℃で１時間撹拌
下に反応した。反応物を１％希硫酸水溶液４２０部に撹
拌下に徐々に排出した。この液を７０℃付近に加熱し、
静置後エチルベンゼン層を分取した。エチルベンゼン層
を中性まで湯洗した後、３％苛性ソーダ水溶液４５０部
を加え、反応生成物を苛性ソーダ水溶液に抽出した。苛
性ソーダ水溶液層を分取し、２０℃以下に冷却し、撹拌
下に希塩酸をｐＨ３になるまで滴下して加えた。析出し
た２−（４−エチルベンゾイル）安息香酸の沈澱を濾
取、水洗後乾燥して白色粉末７４．８部（収率９６．８
％）を得た。融点１２７〜１２９℃、ＬＣ純度９６．２
％であった。[Example 1] Production of 2-ethylanthraquinone (1) Production of 2- (4-ethylbenzoyl) benzoic acid 45 parts of phthalic anhydride was added to 433 parts of ethylbenzene having a water content of 400 ppm at 15 to 20 ° C. It was dispersed by stirring. Under cooling, 81 parts of aluminum chloride was added little by little while maintaining the same temperature. It took about 2 hours to add all the aluminum chloride. After the total amount was added, the reaction was continued at 20 ° C. for 1 hour with stirring. The reaction product was gradually discharged into 420 parts of a 1% dilute sulfuric acid aqueous solution with stirring. Heat this solution to around 70 ° C,
After standing still, the ethylbenzene layer was separated. After washing the ethylbenzene layer with hot water to neutrality, 450 parts of a 3% aqueous sodium hydroxide solution was added, and the reaction product was extracted into the aqueous sodium hydroxide solution. The aqueous solution of caustic soda was separated, cooled to 20 ° C. or lower, and dilute hydrochloric acid was added dropwise with stirring to pH 3. The precipitated 2- (4-ethylbenzoyl) benzoic acid was collected by filtration, washed with water and dried to give 74.8 parts of a white powder (yield 96.8).
%) Was obtained. Melting point 127-129 ° C, LC purity 96.2
%Met.
【００３５】苛性ソーダ水溶液抽出後のエチルベンゼン
層から、水蒸気蒸留によりエチルベンゼン３８０部（回
収率９４．８％）を回収した。回収エチルベンゼンのＧ
Ｃ純度は９９．３％であった。 （２）２−エチルアントラキノンの製造 （１）で製造した２−（４−エチルベンゾイル）安息香
酸７０部を、８％発煙硫酸５７０部に水冷下徐々に添加
溶解後、８５〜８７℃で４時間反応した。反応物を冷却
後水１５００部に排出した。これにトルエン５００部を
添加し、２−エチルアントラキノンの沈澱を溶解抽出し
た。トルエン層を分取、湯洗、希苛性ソーダ水洗後、更
に中性まで湯洗した。トルエンを留去し、黄色の粗製２
−エチルアントラキノン５５．３部（収率８５％）を得
た。From the ethylbenzene layer after extraction of the aqueous caustic soda solution, 380 parts of ethylbenzene (recovery rate 94.8%) was recovered by steam distillation. G of recovered ethylbenzene
The C purity was 99.3%. (2) Production of 2-ethylanthraquinone 70 parts of 2- (4-ethylbenzoyl) benzoic acid produced in (1) was gradually added to 570 parts of 8% fuming sulfuric acid under water cooling and dissolved, followed by 4 at 85 to 87 ° C. Reacted for hours. After cooling the reaction product, it was discharged into 1500 parts of water. To this was added 500 parts of toluene, and the precipitate of 2-ethylanthraquinone was dissolved and extracted. The toluene layer was separated, washed with hot water, washed with dilute caustic soda and then washed with neutral water. Toluene was distilled off and yellow crude 2
55.3 parts (yield 85%) of ethylanthraquinone was obtained.
【００３６】この粗製品５０部を真空蒸留を行い、ｂ．
ｐ．１８５〜１９５℃／３ｍｍＨｇの留分を分取して明
黄色の２−エチルアントラキノン４８．５部を得た。融
点１０９〜１１１℃、ＧＣ純度９９．１％であった。50 parts of this crude product was vacuum distilled, b.
p. A fraction of 185 to 195 ° C./3 mmHg was collected to obtain 48.5 parts of light yellow 2-ethylanthraquinone. The melting point was 109 to 111 ° C and the GC purity was 99.1%.
【００３７】本化合物の赤外吸収スペクトルを図１に示
す。The infrared absorption spectrum of this compound is shown in FIG.
【００３８】下記分析により目的物であることを確認し
た。It was confirmed to be the desired product by the following analysis.
【００３９】質量分析： ２３６（Ｍ+） 元素分析：（Ｃ16Ｈ12Ｏ2） Ｃ Ｈ 測定値： ８２．９％ ５．３％ 計算値： ８１．３％ ５．１％ 本化合物を塩素硫黄分析装置ＴＳＸ−１０型（三菱化成
工業株式会社製）を用いて塩素分を測定したが、未検出
であった。（検出限界０．１ｐｐｍ）Mass analysis: 236 (M + ) Elemental analysis: (C 16 H 12 O 2 ) CH Measured value: 82.9% 5.3% Calculated value: 81.3% 5.1% This compound is chlorine The chlorine content was measured using a sulfur analyzer TSX-10 type (manufactured by Mitsubishi Kasei Co., Ltd.), but it was not detected. (Detection limit 0.1 ppm)
【００４０】［比較例１］ （１）２−（４−エチルベンゾイル）安息香酸の製造 クロルベンゼン２６８部に含水率４００ｐｐｍのエチル
ベンゼン３３．９部と無水フタル酸４５部を加え、１５
〜２０℃で撹拌分散した。これに冷却下、塩化アルミニ
ウム８２．３部を少量づつ同温を保って添加した。塩化
アルミニウムを全量添加するのに約２時間を要した。全
量添加後、更に３５〜４０℃で４時間反応した。塩化ア
ルミニウムは完溶していた。実施例１と同様な方法で後
処理を行い、２−（４−エチルベンゾイル）安息香酸の
白色粉末７３．５部（収率９５．１％）を得た。融点１
２８〜１２９℃、ＬＣ純度９５．７％であった。 （２）２−エチルアントラキノンの製造 上記（１）で製造した２−（４−エチルベンゾイル）安
息香酸７０部を、実施例１−（２）と同様の操作を行っ
て粗製２−エチルアントラキノンを製造した。粗製２−
エチルアントラキノンの収量５４．８部（収率８４．３
％）であった。この粗製品５０部を、実施例１−（２）
と同様にして真空蒸留を行って精製２−エチルアントラ
キノンを得た。精製２−エチルアントラキノンの収量４
８．６部、融点１０９〜１１０℃、ＧＣ純度９８．９％
であった。Comparative Example 1 (1) Production of 2- (4-ethylbenzoyl) benzoic acid To 268 parts of chlorobenzene, 33.9 parts of ethylbenzene having a water content of 400 ppm and 45 parts of phthalic anhydride were added to give 15 parts.
Dispersed with stirring at -20 ° C. Under cooling, 82.3 parts of aluminum chloride was added little by little while maintaining the same temperature. It took about 2 hours to add all the aluminum chloride. After the total amount was added, the reaction was further performed at 35 to 40 ° C. for 4 hours. Aluminum chloride was completely dissolved. Post-treatment was carried out in the same manner as in Example 1 to obtain 73.5 parts (yield 95.1%) of white powder of 2- (4-ethylbenzoyl) benzoic acid. Melting point 1
28-129 degreeC and LC purity was 95.7%. (2) Production of 2-ethylanthraquinone 70 parts of 2- (4-ethylbenzoyl) benzoic acid produced in (1) above were treated in the same manner as in Example 1- (2) to give crude 2-ethylanthraquinone. Manufactured. Crude 2-
Yield of ethylanthraquinone 54.8 parts (yield 84.3
%)Met. 50 parts of this crude product is used in Example 1- (2)
Vacuum distillation was carried out in the same manner as above to obtain purified 2-ethylanthraquinone. Yield of purified 2-ethylanthraquinone 4
8.6 parts, melting point 109-110 ° C, GC purity 98.9%
Met.
【００４１】赤外吸収スペクトルは実施例１−（２）で
製造した精製品のものと同じであった。The infrared absorption spectrum was the same as that of the purified product produced in Example 1- (2).
【００４２】本化合物を塩素硫黄分析装置ＴＳＸ−１０
型を用いて塩素分を測定したところ、３５ｐｐｍであっ
た。This compound was analyzed by chlorine-sulfur analyzer TSX-10.
It was 35 ppm when the chlorine content was measured using the mold.
【００４３】［比較例２］ （１）２−（４−エチルベンゾイル）安息香酸の製造 クロルベンゼン２６８部に含水率４００ｐｐｍのエチル
ベンゼン３３．９部と無水フタル酸４５部を加え、１５
〜２０℃で撹拌分散した。これに冷却下、塩化アルミニ
ウム８２．３部を少量づつ同温を保って添加した。塩化
アルミニウムを全量添加するのに約２時間を要した。全
量添加後、更に２０℃で１時間反応した。実施例１と同
様な方法で後処理を行い、２−（４−エチルベンゾイ
ル）安息香酸の白色粉末６１．９部（収率８０．１％）
を得た。融点１２６〜１２８℃、ＬＣ純度９２．７％で
あった。 （２）２−エチルアントラキノンの製造 上記（１）で製造した２−（４−エチルベンゾイル）安
息香酸６０部を、実施例１−（２）と同様の操作を行っ
て粗製２−エチルアントラキノンを製造した。粗製２−
エチルアントラキノンの収量４４．７部（収率８０．３
％）であった。この粗製品４０部を、実施例１−（２）
と同様にして真空蒸留を行って精製２−エチルアントラ
キノンを得た。精製２−エチルアントラキノンの収量３
１．６部、融点１０９〜１１０℃、ＧＣ純度９８．６％
であった。Comparative Example 2 (1) Production of 2- (4-ethylbenzoyl) benzoic acid To 268 parts of chlorobenzene, 33.9 parts of ethylbenzene having a water content of 400 ppm and 45 parts of phthalic anhydride were added to give 15 parts.
Dispersed with stirring at -20 ° C. Under cooling, 82.3 parts of aluminum chloride was added little by little while maintaining the same temperature. It took about 2 hours to add all the aluminum chloride. After the total amount was added, the reaction was further performed at 20 ° C. for 1 hour. Post-treatment was carried out in the same manner as in Example 1 to obtain 61.9 parts of white powder of 2- (4-ethylbenzoyl) benzoic acid (yield 80.1%).
Got The melting point was 126 to 128 ° C, and the LC purity was 92.7%. (2) Production of 2-ethylanthraquinone 60 parts of 2- (4-ethylbenzoyl) benzoic acid produced in (1) above was treated in the same manner as in Example 1- (2) to give crude 2-ethylanthraquinone. Manufactured. Crude 2-
Yield of ethylanthraquinone 44.7 parts (yield 80.3
%)Met. 40 parts of this crude product was used in Example 1- (2)
Vacuum distillation was carried out in the same manner as above to obtain purified 2-ethylanthraquinone. Yield of purified 2-ethylanthraquinone 3
1.6 parts, melting point 109-110 ° C, GC purity 98.6%
Met.
【００４４】赤外吸収スペクトルは実施例１−（２）で
製造した精製品のものと同じであった。The infrared absorption spectrum was the same as that of the purified product produced in Example 1- (2).
【００４５】本化合物を塩素硫黄分析装置ＴＳＸ−１０
型を用いて塩素分を測定したところ、３３ｐｐｍであっ
た。This compound was analyzed by chlorine-sulfur analyzer TSX-10.
When the chlorine content was measured using a mold, it was 33 ppm.
【００４６】［実施例２］ （１）２−（４−エチルベンゾイル）安息香酸の製造 実施例１−（１）において、塩化アルミニウム添加温度
及びその後の反応温度を３５〜４０℃で行ったほかは、
実施例１と同様に操作を行って、２−（４−エチルベン
ゾイル）安息香酸の白色粉末を得た。[Example 2] (1) Production of 2- (4-ethylbenzoyl) benzoic acid In Example 1- (1), the addition temperature of aluminum chloride and the subsequent reaction temperature were 35 to 40 ° C. Is
The same operation as in Example 1 was performed to obtain a white powder of 2- (4-ethylbenzoyl) benzoic acid.
【００４７】収量：７３．９部（収率９５．７％） 融点：１２７〜１２９℃ ＬＣ純度：９４．０％ エチルベンゼン回収量：３７８部（回収率９４．３％） 回収エチルベンゼンのＧＣ純度：９２．２％ （２）２−エチルアントラキノンの製造 上記（１）で得られた２−（４−エチルベンゾイル）安
息香酸７０部を使用して、実施例１−（２）と同様の操
作を行って粗製２−エチルアントラキノンを製造した。Yield: 73.9 parts (yield 95.7%) Melting point: 127-129 ° C. LC purity: 94.0% Ethylbenzene recovery: 378 parts (recovery rate 94.3%) GC purity of recovered ethylbenzene: 92.2% (2) Production of 2-ethylanthraquinone Using 70 parts of 2- (4-ethylbenzoyl) benzoic acid obtained in (1) above, the same operation as in Example 1- (2) was performed. Performed to produce crude 2-ethylanthraquinone.
【００４８】粗製２−エチルアントラキノンの収量：５
５．１部（収率８４．７％） この粗製品５０部を、実施例１−（２）と同様にして真
空蒸留を行って精製２−エチルアントラキノンを得た。Yield of crude 2-ethylanthraquinone: 5
5.1 parts (yield 84.7%) 50 parts of this crude product was subjected to vacuum distillation in the same manner as in Example 1- (2) to obtain purified 2-ethylanthraquinone.
【００４９】精製２−エチルアントラキノンの収量：４
８．４部 融点：１０９〜１１０℃ ＧＣ純度：９６．２％ 赤外吸収スペクトルは実施例１−（２）で製造したもの
と同じであった。Yield of purified 2-ethylanthraquinone: 4
8.4 parts Melting point: 109-110 ° C GC purity: 96.2% The infrared absorption spectrum was the same as that produced in Example 1- (2).
【００５０】本化合物を塩素硫黄分析装置ＴＳＸ−１０
型を用いて塩素分を測定したところ、未検出であった。This compound was analyzed by chlorine-sulfur analyzer TSX-10.
When the chlorine content was measured using a mold, it was not detected.
【００５１】［実施例３］ （１）２−（４−エチルベンゾイル）安息香酸の製造 実施例１−（１）において、塩化アルミニウムの使用量
を８１部から９０．０部に変えた以外は、実施例１−
（１）と同様の操作を行って、２−（４−エチルベンゾ
イル）安息香酸の白色粉末を得た。Example 3 (1) Production of 2- (4-ethylbenzoyl) benzoic acid Except that the amount of aluminum chloride used in Example 1- (1) was changed from 81 parts to 90.0 parts. Example 1-
The same operation as in (1) was performed to obtain a white powder of 2- (4-ethylbenzoyl) benzoic acid.
【００５２】収量：７６．５部（収率９９．０％） 融点：１２６〜１２８℃ ＬＣ純度：９２．１％ エチルベンゼン回収量：３７０部（回収率９２．３％） 回収エチルベンゼンのＧＣ純度：８８．１％ （２）２−エチルアントラキノンの製造 上記（１）で得られた２−（４−エチルベンゾイル）安
息香酸７０部を使用して、実施例１−（２）と同様の操
作を行って粗製２−エチルアントラキノンを製造した。Yield: 76.5 parts (yield 99.0%) Melting point: 126 to 128 ° C. LC purity: 92.1% Ethylbenzene recovery: 370 parts (recovery rate 92.3%) GC purity of recovered ethylbenzene: 88.1% (2) Production of 2-ethylanthraquinone Using 70 parts of 2- (4-ethylbenzoyl) benzoic acid obtained in the above (1), the same operation as in Example 1- (2) was performed. Performed to produce crude 2-ethylanthraquinone.
【００５３】粗製２−エチルアントラキノンの収量：５
５．７部（収率８５．６％） この粗製品５０部を、実施例１−（２）同様にして真空
蒸留を行って精製２−エチルアントラキノンを得た。Yield of crude 2-ethylanthraquinone: 5
5.7 parts (yield 85.6%) 50 parts of this crude product was subjected to vacuum distillation in the same manner as in Example 1- (2) to obtain purified 2-ethylanthraquinone.
【００５４】精製２−エチルアントラキノンの収量：４
５．２部 融点：１０９〜１１０℃ ＧＣ純度：９５．１％ 赤外吸収スペクトルは実施例１−（２）で製造したもの
と同じであった。Yield of purified 2-ethylanthraquinone: 4
5.2 parts Melting point: 109-110 ° C. GC Purity: 95.1% The infrared absorption spectrum was the same as that produced in Example 1- (2).
【００５５】本化合物を塩素硫黄分析装置ＴＳＸ−１０
型を用いて塩素分を測定したところ、未検出であった。This compound was analyzed by chlorine-sulfur analyzer TSX-10.
When the chlorine content was measured using a mold, it was not detected.
【００５６】［実施例４］ （１）２−（４−エチルベンゾイル）安息香酸の製造 含水率７００ｐｐｍのエチルベンゼン４３３部に無水フ
タル酸４５部を加え、１５〜２０℃で撹拌分散した。こ
れに冷却下、塩化アルミニウム８１部を少量づつ同温を
保って添加しようとしたが、約１３部を添加した時点で
分散していた無水フタル酸と塩化アルミニウムが凝集固
化し、撹拌が困難となった。Example 4 (1) Production of 2- (4-ethylbenzoyl) benzoic acid 45 parts of phthalic anhydride was added to 433 parts of ethylbenzene having a water content of 700 ppm, and the mixture was stirred and dispersed at 15 to 20 ° C. It was attempted to add 81 parts of aluminum chloride little by little while cooling while maintaining the same temperature, but when about 13 parts were added, the dispersed phthalic anhydride and aluminum chloride coagulated and solidified, making stirring difficult. became.
【００５７】同品質のエチルベンゼン４５０部を追加
し、更に１時間撹拌をすると塊状物質は分散した。これ
に添加残の塩化アルミニウム６８部を少量づつ２時間で
添加した。全量添加後、２０℃で更に２時間撹拌した。
不溶分は溶解し均一溶液となった。実施例１−（１）と
同様の操作で後処理を行って、２−（４−エチルベンゾ
イル）安息香酸の白色粉末を得た。When 450 parts of ethylbenzene of the same quality was added and the mixture was further stirred for 1 hour, the lumpy substance was dispersed. 68 parts of the aluminum chloride remaining after the addition was added little by little over 2 hours. After the total amount was added, the mixture was stirred at 20 ° C. for another 2 hours.
The insoluble matter dissolved and became a uniform solution. Post-treatment was carried out in the same manner as in Example 1- (1) to obtain a white powder of 2- (4-ethylbenzoyl) benzoic acid.
【００５８】収量：７５．３部（収率９７．５％） 融点：１２３〜１２８℃ ＬＣ純度：８５．２％ エチルベンゼン回収量：７５７部（回収率８８．５％） 回収エチルベンゼンのＧＣ純度：９８．１％ （２）２−エチルアントラキノンの製造 上記（１）で得られた２−（４−エチルベンゾイル）安
息香酸７０部を使用して、実施例１−（２）と同様の操
作を行って粗製２−エチルアントラキノンを製造した。Yield: 75.3 parts (yield 97.5%) Melting point: 123-128 ° C LC purity: 85.2% Ethylbenzene recovery: 757 parts (recovery rate 88.5%) GC purity of recovered ethylbenzene: 98.1% (2) Production of 2-ethylanthraquinone Using 70 parts of 2- (4-ethylbenzoyl) benzoic acid obtained in (1) above, the same procedure as in Example 1- (2) was performed. Performed to produce crude 2-ethylanthraquinone.
【００５９】粗製２−エチルアントラキノンの収量：５
２．２部（収率８０．３％） この粗製品５０部を、実施例１−（２）同様にして真空
蒸留を行って精製２−エチルアントラキノンを得た。Yield of crude 2-ethylanthraquinone: 5
2.2 parts (yield 80.3%) 50 parts of this crude product was subjected to vacuum distillation in the same manner as in Example 1- (2) to obtain purified 2-ethylanthraquinone.
【００６０】精製２−エチルアントラキノンの収量：４
２．５部 融点：１０７〜１１０℃ ＧＣ純度：９５．１％ 本化合物を塩素硫黄分析装置ＴＳＸ−１０型を用いて塩
素分を測定したところ、未検出であった。Yield of purified 2-ethylanthraquinone: 4
2.5 parts Melting point: 107 to 110 ° C. GC Purity: 95.1% When the chlorine content of this compound was measured using a chlorine-sulfur analyzer TSX-10 type, it was not detected.
【００６１】評価試験 実施例１および比較例１で得た精製２−エチルアントラ
キノンを使用して、過酸水素製造時におけるパラジウム
触媒の安定性を下記の方法で調べた。Evaluation Test Using the purified 2-ethylanthraquinone obtained in Example 1 and Comparative Example 1, the stability of the palladium catalyst during hydrogen peroxide production was examined by the following method.
【００６２】ジイソブチルカルビノール５０ｍＬと１，
２，４−トリメチルベンゼン５０ｍＬの混合溶媒に、２
−エチルアントラキノン１１．８ｇとアルミナ担体の１
％パラジウム触媒（１００〜２００メッシュ）０．１ｇ
を加えて、９０℃で１０時間撹拌した。50 ml of diisobutyl carbinol and 1,
To a mixed solvent of 50 mL of 2,4-trimethylbenzene, 2
-11.8 g of ethylanthraquinone and 1 of alumina carrier
% Palladium catalyst (100-200 mesh) 0.1 g
Was added and stirred at 90 ° C. for 10 hours.
【００６３】この処理液を使用して、下記の方法により
水素の吸収速度を測定した。Using this treatment liquid, the absorption rate of hydrogen was measured by the following method.
【００６４】処理液の入った容器を湯浴により５０℃に
保った。これに、水素消費量が測定でき、かつ水素圧を
常に１気圧に保持できる水素貯めを連結し、処理液を１
気圧の水素でパージした。処理液を１，０００ｒｐｍの
速度で撹拌し、撹拌開始から、２５℃の水素貯めにおい
て５６０ｍＬの水素（使用した２−エチルアントラキノ
ンの０．５倍モル量）が吸収されるまでの時間を測定し
た。The container containing the treatment liquid was kept at 50 ° C. in a water bath. This is connected to a hydrogen reservoir that can measure hydrogen consumption and keep the hydrogen pressure at 1 atm at all times.
Purge with hydrogen at atmospheric pressure. The treatment liquid was stirred at a speed of 1,000 rpm, and the time from the start of stirring until the absorption of 560 mL of hydrogen (0.5 times the molar amount of the used 2-ethylanthraquinone) in the hydrogen storage at 25 ° C. was measured. .
【００６５】結果を表１に示す。The results are shown in Table 1.
【００６６】 ［表１］ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ２−エチルアントラキノン 実施例１で製造した 比較例１で製造した もの もの ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 塩素分含有量 ０．１ｐｐｍ以下 ３５ｐｐｍ ──────────────────────────────────── 水素吸収時間 １２０分 ３１０分 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 水素吸収時間が短いほど、パラジウム触媒の塩素化合物
による被毒が少ないことを示す。[Table 1] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 2-Ethylanthraquinone Example 1 Produced in Comparative Example 1 Produced in Comparative Example 1 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Amount 0.1 ppm or less 35 ppm ──────────────────────────────────── Hydrogen absorption time 120 minutes 310 minutes ━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ The shorter the hydrogen absorption time, the more poisonous the palladium catalyst will be due to chlorine compounds. Is low.
【００６７】[0067]
【発明の効果】本発明の塩素化合物を含有しない２−エ
チルアントラキノンは、共存する薬品、あるいは使用す
る装置、材料に対する悪影響が小さく、染料中間体、紫
外線硬化樹脂あるいはＵＶインキの重合開始剤、あるい
はアントラキノン法過酸化水素製造用媒体として有用な
化合物である。INDUSTRIAL APPLICABILITY The 2-ethylanthraquinone containing no chlorine compound according to the present invention has a small adverse effect on coexisting chemicals, used equipment and materials, and is a dye intermediate, an ultraviolet curable resin or a polymerization initiator for UV ink, or It is a compound useful as a medium for anthraquinone method hydrogen peroxide production.
【図１】実施例１で製造した精製２−エチルアントラキ
ノンの赤外吸収スペクトルである。FIG. 1 is an infrared absorption spectrum of purified 2-ethylanthraquinone produced in Example 1.
Claims (9)
チルアントラキノン。1. 2-Ethylanthraquinone which is substantially free of chlorine compounds.
項１に記載の２−エチルアントラキノン。2. The 2-ethylanthraquinone according to claim 1, which has a chlorine content of 1 ppm or less.
塩化アルミニウムの存在下に製造された２−（４−エチ
ルベンゾイル）安息香酸を使用して製造された、請求項
１または２に記載の２−エチルアントラキノン。3. 2-Ethyl according to claim 1, which is prepared by using 2- (4-ethylbenzoyl) benzoic acid prepared in the presence of aluminum chloride from ethylbenzene and phthalic anhydride alone. Anthraquinone.
塩化アルミニウムの存在下に製造された２−（４−エチ
ルベンゾイル）安息香酸を環化する、請求項１または２
に記載の２−エチルアントラキノンの製造方法。4. The cyclization of 2- (4-ethylbenzoyl) benzoic acid produced in the presence of aluminum chloride from ethylbenzene and phthalic anhydride alone.
The method for producing 2-ethylanthraquinone according to 1.
塩化アルミニウムの存在下に２−（４−エチルベンゾイ
ル）安息香酸を製造し、次いでこの２−（４−エチルベ
ンゾイル）安息香酸を発煙硫酸の存在下に環化する、請
求項１または２に記載の２−エチルアントラキノンの製
造方法。5. 2- (4-Ethylbenzoyl) benzoic acid is produced from ethylbenzene and phthalic anhydride in the presence of aluminum chloride, and the 2- (4-ethylbenzoyl) benzoic acid is then produced in the presence of fuming sulfuric acid. The method for producing 2-ethylanthraquinone according to claim 1 or 2, which is cyclized to.
０ｐｐｍ以下である請求項４または５に記載の製造方
法。6. The water content of ethylbenzene used is 50.
The production method according to claim 4 or 5, which is 0 ppm or less.
部に対して１.７〜２.０重量部使用する請求項４〜６の
いずれかに記載の製造方法。7. The production method according to claim 4, wherein 1.7 to 2.0 parts by weight of aluminum chloride is used with respect to 1 part by weight of phthalic anhydride.
を製造する際の反応温度が０〜４０℃である請求項４〜
７のいずれかに記載の製造方法。8. The reaction temperature for producing 2- (4-ethylbenzoyl) benzoic acid is 0 to 40 ° C.
7. The manufacturing method according to any one of 7.
を製造する際の反応時間が、塩化アルミニウムを全量添
加完了後２０分〜４時間である請求項４〜８のいずれか
に記載の製造方法。9. The production according to claim 4, wherein the reaction time in producing 2- (4-ethylbenzoyl) benzoic acid is 20 minutes to 4 hours after the addition of the entire amount of aluminum chloride is completed. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29129593A JPH07118195A (en) | 1993-10-26 | 1993-10-26 | 2-ethylanthraquinone and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29129593A JPH07118195A (en) | 1993-10-26 | 1993-10-26 | 2-ethylanthraquinone and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07118195A true JPH07118195A (en) | 1995-05-09 |
Family
ID=17767042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29129593A Pending JPH07118195A (en) | 1993-10-26 | 1993-10-26 | 2-ethylanthraquinone and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07118195A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010105942A (en) * | 2008-10-29 | 2010-05-13 | Yamamoto Chem Inc | Anthraquinone composition and method for producing the same |
| JP2014224009A (en) * | 2013-05-16 | 2014-12-04 | 三菱瓦斯化学株式会社 | Actuating solution used for hydrogen peroxide production, processing method of the same, and method of hydrogen peroxide production using the same |
| CN108982750A (en) * | 2018-07-09 | 2018-12-11 | 湖州吉昌化学有限公司 | The detection method of chlorinity in a kind of 2- ethyl hydrazine |
| CN111747839A (en) * | 2020-06-24 | 2020-10-09 | 潍坊门捷化工有限公司 | Synthetic method of 2- (4' -ethylbenzoyl) benzoic acid |
| CN116120161A (en) * | 2022-12-28 | 2023-05-16 | 宜昌苏鹏科技有限公司 | Process for treating rectification residues of 2-ethyl anthraquinone and recovering 2-ethyl anthraquinone |
-
1993
- 1993-10-26 JP JP29129593A patent/JPH07118195A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010105942A (en) * | 2008-10-29 | 2010-05-13 | Yamamoto Chem Inc | Anthraquinone composition and method for producing the same |
| JP2014224009A (en) * | 2013-05-16 | 2014-12-04 | 三菱瓦斯化学株式会社 | Actuating solution used for hydrogen peroxide production, processing method of the same, and method of hydrogen peroxide production using the same |
| CN108982750A (en) * | 2018-07-09 | 2018-12-11 | 湖州吉昌化学有限公司 | The detection method of chlorinity in a kind of 2- ethyl hydrazine |
| CN111747839A (en) * | 2020-06-24 | 2020-10-09 | 潍坊门捷化工有限公司 | Synthetic method of 2- (4' -ethylbenzoyl) benzoic acid |
| CN116120161A (en) * | 2022-12-28 | 2023-05-16 | 宜昌苏鹏科技有限公司 | Process for treating rectification residues of 2-ethyl anthraquinone and recovering 2-ethyl anthraquinone |
| CN116120161B (en) * | 2022-12-28 | 2024-04-05 | 宜昌苏鹏科技有限公司 | Process for treating 2-ethylanthraquinone distillation residue and recovering 2-ethylanthraquinone |
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