WO2010104028A1 - 電気分解を利用した芳香族ハロゲン化合物の製造方法 - Google Patents
電気分解を利用した芳香族ハロゲン化合物の製造方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/27—Halogenation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
Definitions
- the present invention relates to a method for producing an aromatic halogen compound, and more particularly, to a method for producing an aromatic halogen compound from an aromatic compound by electrolysis using a transition metal catalyst and a halogenating agent.
- a halogenation reaction using a halogenating agent as described above in the presence of a palladium catalyst has also been developed (see, for example, non-patent documents 2 to 4).
- a stoichiometric amount of a halogenating agent it is necessary to use a stoichiometric amount of a halogenating agent, and there is a problem that it is difficult to work up the reaction and control the reactivity.
- An object of the present invention is to provide a novel process for producing aromatic halogen compounds, which solves the problems in the prior art.
- the present inventors supply water to the cathode chamber in an electrolytic cell partitioned by an anion exchange membrane, and aromatic compounds, polar organic solvents and cases to the anode chamber. It has been found that halogen is introduced onto the aromatic ring of the aromatic compound to produce an aromatic halogen compound by supplying a transition metal catalyst by means of electrolysis and performing electrolysis in the presence of a halogenating agent. We came to complete the invention.
- the present invention 1.
- water is supplied to the cathode chamber, the aromatic compound and the polar organic solvent are supplied to the anode chamber, and the electrolysis is carried out in the presence of a halogenating agent to obtain the aroma.
- a method for producing an aromatic halogen compound which comprises introducing a halogen onto an aromatic ring of a group compound. 2.
- the halogenating agent is hydrogen halide, which is supplied to the cathode chamber; Manufacturing method described. 3.
- the halogenating agent is hydrogen chloride or hydrogen bromide. Manufacturing method described. 4.
- the halogenating agent is a combination of an alkali metal halide salt and a strong acid selected from sulfuric acid or nitric acid, and the alkali metal halide salt is supplied to the anode chamber and the strong acid is supplied to the cathode chamber.
- the halogenating agent is a combination of potassium iodide and sulfuric acid, Manufacturing method described. 6.
- the electrolysis is carried out in the presence of a transition metal catalyst supplied to the anode compartment, To 5. Manufacturing method described. 7. 5. the transition metal catalyst is a palladium catalyst, Manufacturing method described. 8.
- the aromatic compound is an aromatic hydrocarbon compound selected from benzene, biphenyl, naphthalene, biphenylene, and phenanthrene, or an aromatic heterocyclic compound selected from benzoquinoline and phenanthridine.
- An aromatic compound is a compound in which an aromatic hydrocarbon compound and an aromatic heterocyclic compound are bonded by a single bond.
- Aromatic compounds are selected from 2-phenylpyridines, 2- (1-naphthyl) pyridines, 2-phenyl pyrimidines, 2- (1-naphthyl) pyrimidines, 1-phenylisoquinolines and 2-phenylquinolines Above, 9. Manufacturing method described. About.
- halogen can be introduced regioselectively onto the aromatic ring.
- the halogenating agent it is possible to use an inexpensive and easy-to-handle hydrogen chloride such as hydrogen chloride, hydrogen bromide such as hydrogen bromide, a halogenated alkali metal salt, a strong acid such as sulfuric acid or nitric acid.
- the halogen ion of the halogenating agent is converted to a halogenium ion in the system by the electrochemical method and the reaction proceeds, the high reactivity after the reaction is different from the conventional method.
- the product can be separated simply by separating the reaction solution using water and an organic solvent (diethyl ether, ethyl acetate etc.), and the high-purity product is obtained in high yield by simple separation operation.
- an organic solvent diethyl ether, ethyl acetate etc.
- aromatic compound used as a raw material in the present invention refers to a monocyclic or polycyclic aromatic hydrocarbon compound or aromatic heterocyclic compound.
- aromatic compound as a raw material in the present invention is not particularly limited as long as it has a site at which halogenation can occur, ie, at least one carbon-hydrogen bond on an aromatic ring.
- the aromatic hydrocarbon compound is not particularly limited, and examples thereof include benzene, biphenyl, indene, indane, naphthalene, biphenylene, acenaphthylene, phenanthrene, anthracene, pyrene and the like, with preference given to benzene, biphenyl, Naphthalene, biphenylene and phenanthrene.
- the aromatic heterocyclic compound is a compound in which one or more atoms other than carbon atoms (eg, oxygen, sulfur, nitrogen, etc.) are contained in the atoms constituting the ring system of the aromatic hydrocarbon compound.
- atoms other than carbon atoms eg, oxygen, sulfur, nitrogen, etc.
- a compound in which the above aromatic hydrocarbon compound and the above aromatic heterocyclic compound are bonded by a single bond is also a preferable compound, and examples thereof include 2-phenylpyridines, 2- (1-naphthyl) pyridines, and 2-phenyl Pyrimines, 2- (1-naphthyl) pyrimidines, 1-phenylisoquinolines and 2-phenylquinolines are included.
- aromatic compounds can have a substituent within the range not inhibiting the reaction of the present invention, and as such a substituent, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a haloalkyl group, a haloalkoxy group can be mentioned And halogen atoms, hydroxy groups, formyl groups, cyano groups, nitro groups, sulfonyl groups, carboxy groups, nitro groups, amino groups, acetyl groups, acetoxy groups, thioalkoxy groups and the like.
- aromatic compound to be particularly preferably used include the following: (Here, R is hydrogen, an alkyl group, an alkoxy group, a haloalkyl group, a haloalkoxy group, a halogen atom, a cyano group or an alkoxycarbonyl group).
- halogenating agent to be used in the present invention is not particularly limited, but hydrogen halide, phosphorus phosphorus, triphenylphosphine phosphonate, alkyl halide, sulfonyl halide, thionyl halide, acid halogen And halogenated halogen compounds such as boron halides and silicon halides; alkali metal halides; metal halides such as titanium halides and tin halides; It can be used in combination with a strong acid selected from sulfuric acid or nitric acid.
- the halogenating agent is usually supplied to the cathode chamber, but when using a combination of an alkali metal halide salt and a strong acid selected from sulfuric acid or nitric acid as the halogenating agent, the alkali metal halide salt is supplied to the anode chamber And supply a strong acid to the cathode chamber.
- a hydrogen halide such as hydrogen chloride, hydrogen bromide or hydrogen iodide
- particularly preferably hydrogen chloride or hydrogen bromide can be used.
- alkali metal halide salts such as halides of potassium can be used in combination with the strong acid, and particularly preferably potassium iodide can be used.
- the amount of the halogenating agent used is usually 2 to 200 mol, preferably 4 to 100 mol, and dissolved at a concentration of 0.5 to 5 mol / L, preferably 1 to 3 mol / L, relative to 1 mol of the aromatic compound. Used in solution.
- the concentration of the strong acid is 0.05 to 2 mol / L, preferably 0.1 to 0.5 mol / L
- the amount of the halogenating agent used is 1 mol of the aromatic compound.
- it is used in a solution dissolved in a concentration of 1 to 10 mol, preferably 2 to 4 mol, at a concentration of 0.01 to 1 mol / L, preferably 0.02 to 0.1 mol / L.
- the “transition metal catalyst” used in the present invention is not particularly limited, and nickel, palladium, platinum, cobalt, rhodium, iridium, iron, ruthenium, osmium, copper, silver, gold, etc., and salts thereof Compounds such as and complexes can be used.
- Preferred transition metal catalysts are palladium catalysts, and metals, salts and complexes can be used, and particularly preferred are palladium chloride, palladium bromide, palladium acetate and the like which are readily available.
- the amount of transition metal catalyst used is usually 0.2 to 100 mol%, preferably 2 to 20 mol%.
- an alkali metal carbonate for example, K 2 CO 3 may be added to improve the reactivity.
- Electron rich aromatic compounds such as toluene are halogenated even under non-catalytic conditions.
- the “polar organic solvent” used in the present invention is not particularly limited as long as it is a polar organic solvent in which an aromatic compound as a substrate is dissolved, and examples thereof include N, N-dimethylformamide (DMF), dimethylacetamide (DMA), Dimethyl sulfoxide (DMSO), acetonitrile, N-methyl-2-pyrrolidone (NMP), hexamethylphosphoramide (HMPA), N, N, N ', N'-tetramethylurea (TMU), etc., or a mixture thereof Can be used.
- the aromatic compound is usually dissolved in a polar organic solvent at a concentration of 0.01 to 1 mol / L, preferably 0.02 to 0.5 mol / L.
- the method of the present invention is characterized in that it is carried out in a positive / negative electrode separation type electrolytic cell partitioned by an anion exchange membrane.
- the anion exchange membrane is not particularly limited, and a strong base or weak base commercially available membrane can be appropriately used.
- the strongly basic type is more preferable, and specific examples thereof include Seremion AHA (manufactured by Asahi Glass Co., Ltd.), Neosepta AHA (manufactured by Astom Co., Ltd.), and the like.
- the electrode material is not particularly limited as long as it is acid resistant, and conventionally known materials can be widely used. For example, platinum, glass carbon, carbon, stainless steel, nickel, other processed electrodes, etc. It can be used.
- the current density is usually selected appropriately from the range of 0.1 to 100 mA / cm 2 , preferably 1 to 50 mA / cm 2 , particularly preferably 10 to 20 mA / cm 2 . is there.
- the amount of electricity supplied is usually 1 to 40 F, preferably 1.5 to 25 F, per mole of the aromatic compound.
- the reaction time is appropriately selected from the current to be supplied, the current density and the like, and is usually within 24 hours.
- the reaction temperature is usually 40 to 100 ° C., preferably 70 to 100 ° C.
- the process of the invention can also be carried out either batchwise or continuously.
- a pure product can be obtained only by performing a liquid separation operation using water and an organic solvent (eg, diethyl ether, ethyl acetate, etc.) after completion of the reaction.
- an organic solvent eg, diethyl ether, ethyl acetate, etc.
- the halogen is regioselectively introduced onto the aromatic ring of the aromatic compound.
- the halogen is introduced.
- a compound in which a phenyl group is substituted at the 2-position of the pyridine ring as shown below, regioselectively at the position of ⁇ with respect to the position of the pyridine nitrogen without being affected by the substituent on the aromatic ring Halogen is introduced.
- reaction conditions such as a catalyst, a current value, and a reaction time
- reaction conditions such as a catalyst, a current value, and a reaction time
- FIG. 1 is a schematic view showing a method for producing an aromatic halogen compound of the present invention.
- the electrolytic cell 1 is composed of an anode chamber 2 and a cathode chamber 3 and an anion exchange membrane 4 separating them.
- a platinum electrode 5 is inserted into the anode chamber 2 and the cathode chamber 3, and a stirrer 6 is inserted into the anode chamber 2.
- An aqueous solution in which a halogenating agent (hydrogen halide: HX) is dissolved is supplied to the cathode chamber 3, and an aromatic compound as a substrate, a polar organic solvent and optionally a transition metal catalyst are supplied to the anode chamber 2.
- the electrolysis is performed while the anode chamber is stirred by the stirrer 6.
- a halogenium ion is generated in the anode chamber 2 and a halogen is introduced onto the aromatic ring from which the carbon-hydrogen bond has been broken.
- FIG. 2 is also schematic which shows the manufacturing method of the aromatic halogen compound of this invention.
- the electrolytic cell 1 is composed of an anode chamber 2 and a cathode chamber 3 and an anion exchange membrane 4 separating them.
- a platinum electrode 5 is inserted into the anode chamber 2 and the cathode chamber 3, and a stirrer 6 is inserted into the anode chamber 2.
- An aqueous solution in which a strong acid is dissolved is supplied to the cathode chamber 3, and an aromatic compound as a substrate, a polar organic solvent, a halogenating agent (alkali metal halide salt: MeX) and optionally a transition metal catalyst are supplied to the anode chamber 2.
- a halogenating agent alkali metal halide salt: MeX
- the electrolysis is performed while the anode chamber is stirred by the stirrer 6.
- a halogenium ion is generated in the anode chamber 2 and a halogen is introduced onto the aromatic ring from which the carbon-hydrogen bond has been broken.
- Example 1 The anion exchange membrane (Astom, Neosepta AHA) was washed with pure water, methanol and acetone, and cut out according to the size of the space holder. Subsequently, using the cut out ion exchange membrane, a positive / negative electrode separation type electrolytic cell was assembled.
- the anode compartment is benzo [h] quinoline (44.8mg, 0.25mmol), PdCl 2 (4.4mg, 0.025mmol), DMF and (10ml), the cathode compartment was added 2M HCl aq (10ml) . Thereafter, the electrolytic cell was placed in an oil bath heated to 90 ° C. and stirred for 2.5 hours while applying a current of 20 mA using a platinum electrode. The reaction was followed by GCMS to confirm that after 2 hours all the material was consumed.
- reaction system was cooled to room temperature. After pouring a saturated aqueous solution of K 2 CO 3 into the anode chamber for neutralization, it was washed into a separatory funnel with AcOEt and water. The organic and aqueous layers were separated, and the aqueous layer was extracted twice with AcOEt. All organic layers were combined, washed twice with water and once with saturated brine, dried over anhydrous Na 2 SO 4 and concentrated on a rotary evaporator.
- Example 2 to 16 The same reaction as in Example 1 was carried out except that the reaction temperature and the reaction time were changed as shown in Table 1 below (in Example 14 only, current was applied at 10 mA). The yield of the target compound is shown in Table 1.
- Examples 17 to 19 10 mol% PdBr using 2 (Example 19 only 15 mol% PdBr 2) as the transition metal catalyst, by using a 2M HBr aqueous solution as the halogenating agent, except for changing the reaction temperature and reaction time as shown in Table 2, embodiment The same reaction as in Example 1 was carried out (only Example 18 was energized at 10 mA). The yield of the target compound is shown in Table 2.
- Example 24 The following reactions were performed. Except the conditions shown below, it is the same as that of Example 1. The results are shown in Table 3 below.
- Non-catalytic reaction Example 25 The following reaction was carried out without catalyst. Except the conditions shown below, it is the same as that of Example 1.
- aromatic halogen compounds useful as starting compounds for agricultural chemicals, medicines, and fine chemicals such as organic electronic materials and organic optical materials can be produced efficiently, selectively and under reaction conditions with low environmental load. Therefore, it is extremely useful for industrial production of products in these fields.
- Electrolyzer 2 ... anode chamber, 3 ... cathode chamber, 4 ... Anion exchange membrane, 5 ... platinum electrode, 6 ... stirrer, 7 ... anode, 8 ⁇ ⁇ ⁇ Cathode
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Abstract
Description
1.陰イオン交換膜で区画した電解槽において、陰極室に水を供給し、陽極室に芳香族化合物および極性有機溶媒を供給して、ハロゲン化剤の存在下に電気分解を行うことにより、該芳香族化合物の芳香環上へハロゲンを導入することを特徴とする、芳香族ハロゲン化合物の製造方法。
2.ハロゲン化剤がハロゲン化水素であり、これを陰極室に供給する、上記1.記載の製造方法。
3.ハロゲン化剤が塩化水素または臭化水素である、上記2.記載の製造方法。
4.ハロゲン化剤がハロゲン化アルカリ金属塩と硫酸または硝酸から選ばれる強酸との組み合わせであり、ハロゲン化アルカリ金属塩を陽極室に供給し、強酸を陰極室に供給する、上記1.記載の製造方法。
5.ハロゲン化剤がヨウ化カリウムと硫酸との組み合わせである、4.記載の製造方法。
6.電気分解を陽極室に供給した遷移金属触媒の存在下に行う、1.~5.記載の製造方法。
7.遷移金属触媒がパラジウム触媒である、6.記載の製造方法。
8.芳香族化合物が、ベンゼン、ビフェニル、ナフタレン、ビフェニレン、およびフェナントレンから選択される芳香族炭化水素化合物またはベンゾキノリンおよびフェナントリジンから選択される芳香族複素環式化合物である、上記1.~7.のいずれか記載の製造方法。
9.芳香族化合物が、芳香族炭化水素化合物と芳香族複素環式化合物が単結合で結合した化合物である、上記1.~7.のいずれか記載の製造方法。
10.芳香族化合物が、2-フェニルピリジン類、2-(1-ナフチル)ピリジン類、2-フェニルピリミジン類、2-(1-ナフチル)ピリミジン類、1-フェニルイソキノリン類および2-フェニルキノリン類から選択される、上記9.記載の製造方法。
に関する。
(ここで、Rは水素、アルキル基、アルコキシ基、ハロアルキル基、ハロアルコキシ基、ハロゲン原子、シアノ基またはアルコキシカルボニル基である)。
陰イオン交換膜としては、特に限定されず、強塩基性型または弱塩基性型の市販のものを適宜使用することができる。強塩基性型がより好ましく、具体的には、セレミオンAHA(旭硝子社製)、ネオセプタAHA(アストム社製)等が挙げられる。
以下に、本発明の実施例を詳細に説明する。
得られた10-クロロベンゾ[h]キノリンの1H-NMRスペクトルは以下の通りである。1H NMR (270.05 MHz) (CDCl3) : δ 7.31-7.50 (m, 5H, 4), 7.53 (d, J = 8.7 Hz, 1H, 3), 7.78-7.90 (m, 3H, 2), 8.81 (d, J = 4.3 Hz, 1H, 1)。
遷移金属触媒として10mol% PdBr2(実施例19のみ15mol% PdBr2)を用い、ハロゲン化剤として2M HBr水溶液を用いて、下記表2に示すとおり反応温度および反応時間を変更した以外は、実施例1と同様の反応を行った(実施例18のみ10mAで通電)。目的化合物の収率を表2に示す。
Claims (10)
- 陰イオン交換膜で区画した電解槽において、陰極室に水を供給し、陽極室に芳香族化合物および極性有機溶媒を供給して、ハロゲン化剤の存在下に電気分解を行うことにより、該芳香族化合物の芳香環上へハロゲンを導入することを特徴とする、芳香族ハロゲン化合物の製造方法。
- ハロゲン化剤がハロゲン化水素であり、これを陰極室に供給する、請求項1記載の製造方法。
- ハロゲン化剤が塩化水素または臭化水素である、請求項2記載の製造方法。
- ハロゲン化剤がハロゲン化アルカリ金属塩と硫酸または硝酸から選ばれる強酸との組み合わせであり、ハロゲン化アルカリ金属塩を陽極室に供給し、強酸を陰極室に供給する、請求項1記載の製造方法。
- ハロゲン化剤がヨウ化カリウムと硫酸との組み合わせである、請求項4記載の製造方法。
- 電気分解を陽極室に供給した遷移金属触媒の存在下に行う、請求項1~5記載の製造方法。
- 遷移金属触媒がパラジウム触媒である、請求項6記載の製造方法。
- 芳香族化合物が、ベンゼン、ビフェニル、ナフタレン、ビフェニレン、およびフェナントレンから選択される芳香族炭化水素化合物またはベンゾキノリンおよびフェナントリジンから選択される芳香族複素環式化合物である、請求項1~7のいずれか1項記載の製造方法。
- 芳香族化合物が、芳香族炭化水素化合物と芳香族複素環式化合物が単結合で結合した化合物である、請求項1~7のいずれか1項記載の製造方法。
- 芳香族化合物が、2-フェニルピリジン類、2-(1-ナフチル)ピリジン類、2-フェニルピリミジン類、2-(1-ナフチル)ピリミジン類、1-フェニルイソキノリン類および2-フェニルキノリン類から選択される、請求項9記載の製造方法。
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US13/203,597 US20110308963A1 (en) | 2009-03-10 | 2010-03-08 | Process for producing aromatic halogen compound utilizing electrolysis |
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- 2010-03-08 WO PCT/JP2010/053766 patent/WO2010104028A1/ja active Application Filing
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JPS5751272A (en) * | 1980-09-11 | 1982-03-26 | Sugai Kagaku Kogyo Kk | Production of 2,4-dichloralkoxybenzene |
JPS5861285A (ja) * | 1981-10-07 | 1983-04-12 | Sugai Kagaku Kogyo Kk | トルエンの塩素化方法 |
JPS59143081A (ja) * | 1983-02-02 | 1984-08-16 | Kohjin Co Ltd | チモールのハロゲン化合物の製造方法 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2024043158A1 (ja) * | 2022-08-25 | 2024-02-29 | 国立大学法人横浜国立大学 | 環状アミンの製造装置及び環状アミンの製造方法 |
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