JPS6341434A - Production of 3,4'-dichlorodiphenyl ether - Google Patents
Production of 3,4'-dichlorodiphenyl etherInfo
- Publication number
- JPS6341434A JPS6341434A JP61184249A JP18424986A JPS6341434A JP S6341434 A JPS6341434 A JP S6341434A JP 61184249 A JP61184249 A JP 61184249A JP 18424986 A JP18424986 A JP 18424986A JP S6341434 A JPS6341434 A JP S6341434A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- ether
- sodium
- dichlorobenzene
- chlorophenolate
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- HPRGYUWRGCTBAV-UHFFFAOYSA-N 1-chloro-3-(4-chlorophenoxy)benzene Chemical compound C1=CC(Cl)=CC=C1OC1=CC=CC(Cl)=C1 HPRGYUWRGCTBAV-UHFFFAOYSA-N 0.000 title description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 6
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 5
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 claims description 7
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 150000001983 dialkylethers Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 abstract description 8
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 abstract description 6
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 abstract description 6
- -1 aliphatic glycol dialkyl ether Chemical class 0.000 abstract description 5
- 239000001103 potassium chloride Substances 0.000 abstract description 4
- 235000011164 potassium chloride Nutrition 0.000 abstract description 4
- 239000011261 inert gas Substances 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- CFPLEOLETMZLIB-UHFFFAOYSA-M sodium;4-chlorophenolate Chemical compound [Na+].[O-]C1=CC=C(Cl)C=C1 CFPLEOLETMZLIB-UHFFFAOYSA-M 0.000 abstract 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 150000001555 benzenes Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000002170 ethers Chemical class 0.000 description 6
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001447 alkali salts Chemical class 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 229940045803 cuprous chloride Drugs 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000003352 sequestering agent Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- VSKSUBSGORDMQX-UHFFFAOYSA-N 1,2-dichloro-3-phenoxybenzene Chemical compound ClC1=CC=CC(OC=2C=CC=CC=2)=C1Cl VSKSUBSGORDMQX-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- RHMPLDJJXGPMEX-UHFFFAOYSA-N 4-fluorophenol Chemical compound OC1=CC=C(F)C=C1 RHMPLDJJXGPMEX-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 238000006959 Williamson synthesis reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 229940076286 cupric acetate Drugs 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical group CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 230000021148 sequestering of metal ion Effects 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は農薬、医薬及び高機能性高分子材料など広範な
分野に用いられている３、４１−ジアミノジフェニルエ
ーテルの中間体と成り得る３、４’ −ジクロロジフェ
ニルエーテルの製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to 3,4' which can be an intermediate for 3,41-diaminodiphenyl ether, which is used in a wide range of fields such as agricultural chemicals, medicines, and highly functional polymer materials. -This invention relates to a method for producing dichlorodiphenyl ether.
従来技術
従来、ジフェニルエーテル類の合成法としてフェノール
とハロゲン化ベンゼンをアルカリ塩存在下反応させるウ
ィリアムソン（Ｗｉｌｌｉａｎｌｓｏｎ ）反応が知ら
れている。この反応を極性溶媒中性なうと反応温度を低
下させることが出来るが容易に反応が進行するのは活性
化されたハロゲン化ベンゼンの場合のみであり、活性の
低いハロゲン化ベンゼンでは目的の化合物はほとんど得
られない。BACKGROUND ART Conventionally, the Williamson reaction, in which phenol and halogenated benzene are reacted in the presence of an alkali salt, has been known as a method for synthesizing diphenyl ethers. The reaction temperature can be lowered by neutralizing the polar solvent, but the reaction progresses easily only in the case of activated halogenated benzene, and with less active halogenated benzene, the target compound cannot be produced. Almost no gain.
一方、フェノールのアルカリ塩とハロゲン化ベンゼンと
の反応で高温で銅もしくは銅塩存在下反応させるウルマ
ン（ｊＪ Ｉｌｍａｎｎ）反応も知られているが、活性
の低いジクロロベンゼンとクロロフェノールのアルカリ
塩とは、銅や銅塩存在下でも反応しない。つまり、ハロ
ゲン化ベンゼンはフェノラートを溶解せしめる能力もな
いし銅塩を反応活性型に変えることら出来ないと考えら
れる。そこで、クロロフェノールを過剰に加え溶媒とし
て用い反応させる例（特開昭４９−６２４３４号公＋Ｆ
ｉ）もあるが、ジフェニルエーテルの収率はかならずし
も高くむい。さらに不活性なハロゲン化ベンゼンの反応
で金属イオン封鎖剤を入れ反応させろ例（時間１ｉｄ（
５Ｇ−２９５３９号公報）もあるが高価な金属封鎖剤を
用いなければならない。On the other hand, the Ullmann reaction is known, in which an alkali salt of phenol reacts with a halogenated benzene at high temperature in the presence of copper or a copper salt, but the reaction between dichlorobenzene and an alkali salt of chlorophenol, which have low activity, is known. , does not react even in the presence of copper or copper salts. In other words, it is thought that halogenated benzene has neither the ability to dissolve phenolate nor convert copper salt into a reactive form. Therefore, an example of adding chlorophenol in excess and using it as a solvent for the reaction (JP-A-49-62434+F
Although there is also i), the yield of diphenyl ether is not necessarily high. Furthermore, in the reaction of inert halogenated benzene, add a metal ion sequestering agent and let it react (time 1 id (
5G-29539), but it requires the use of an expensive metal sequestering agent.
本発明者らは種々の研究の結果、ｐ−クロロフェノール
のナトリウム塩とｍ−ジクロロベンゼンを銅触媒存在下
反応条件下で液状を呈する脂肪族グリコールのジアルキ
ルエーテルを存在せしめて反応せしめると（ｔめて高収
率で３．４′ −ジクロロジフェニルエーテルが１募ら
れることを見い出し本発明に至った。As a result of various studies, the present inventors have found that when sodium salt of p-chlorophenol and m-dichlorobenzene are reacted in the presence of a dialkyl ether of aliphatic glycol, which is liquid under reaction conditions in the presence of a copper catalyst, (t It has been discovered that 3,4'-dichlorodiphenyl ether can be obtained in high yield for the first time, leading to the present invention.
発明の構成
本発明はｐ−クロロフェノールのナトリウム塩とｍ−ジ
クロロベンゼンとを反応条件下で液状をデする脂肪族グ
リコールのジアルキルエーテル及び銅触媒の存在下反応
させることを特徴とする３、４′ −ジクロロフェニル
エーテルの製造法である。Structure of the Invention The present invention is characterized in that sodium salt of p-chlorophenol and m-dichlorobenzene are reacted under reaction conditions in the presence of a dialkyl ether of an aliphatic glycol that makes the liquid state and a copper catalyst. ′-Dichlorophenyl ether production method.
本発明の方法に使用される前記エーテルとしては種々の
巳のが）重用出来る。As the ether used in the method of the present invention, various ethers can be used.
その例としては、一般式Ｒ＋ Ｃｏ Ｒ］ｎ○−Ｒ
２で表わされるエーテルが好ましい。ここでＲはメチレ
ン、エチレン、プロピレン、ブチレンの如き炭素数１〜
４のアルキレンであり、好ましくはエチレンまたはプロ
ピレンである。またＲ１とＲ２は同一もしくは異なり、
炭素数１〜４の低級アルキル基を示し、ｎは１以上の整
数を示す。As an example, the general formula R+ Co R]n○-R
Ethers represented by 2 are preferred. Here, R has 1 to 1 carbon atoms such as methylene, ethylene, propylene, butylene.
4, preferably ethylene or propylene. Also, R1 and R2 are the same or different,
It represents a lower alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 or more.
本発明のかかる脂肪族グリコールのジアルキルエーテル
の具体例としては、その脂肪族グリコール骨格がエチレ
ングリコール、ジエチレングリコール、トリエチレング
リコールまたはテ１〜ラエチレングリコールであり、こ
れらのジメチル−、ジエチル−、ジプロピル−またはジ
ブチル−エーテルが好ましいものとして挙げられる。一
方比較例に示した通り他のエーテル化合物を用いても目
的とする３、４′ −ジクロロジフェニルエーテルを高
収率で得ることはできない。Specific examples of the dialkyl ether of aliphatic glycol according to the present invention include those whose aliphatic glycol skeleton is ethylene glycol, diethylene glycol, triethylene glycol, or tetraethylene glycol, and dimethyl-, diethyl-, dipropyl- Or dibutyl-ether is mentioned as a preferable one. On the other hand, as shown in the comparative example, even if other ether compounds are used, the desired 3,4'-dichlorodiphenyl ether cannot be obtained in high yield.
これらのエーテルは単独または２種類以上を混合しても
用いることが出来る。これらエーテルの使用量はｐ−ク
ロロフェノールのナトリウム金属塩に対して０．５〜２
０倍当間の範囲で十分良好な効果が得られるが好ましく
は１〜５倍当最の範囲である。反応に用いられる銅触媒
としては、金属銅（Ｃｕ）、（：、ｕ ｏ、ＣＩＪ ２
０．Ｃｕ（Ｊ、ＣＬＩＣｊ２・２Ｈ２０，酢酸第二銅（
ＣＩＪ （ＯＡＣ）２ ・Ｒ２０）等を好適な例と
してあげられるが、その他の銅化合物でめってもこの反
応に用いることが出来る。銅触媒の間はｐ−クロロフェ
ノールのナトリウム金属塩を基１％ｉとにして０．００
１〜１．０倍当量であり、好ましくはｏ、ｏｏｓ〜０．
１０倍当量である。These ethers can be used alone or in combination of two or more. The amount of these ethers used is 0.5 to 2
Sufficiently good effects can be obtained within the range of 0 times, but preferably the range is 1 to 5 times. The copper catalyst used in the reaction includes metallic copper (Cu), (:, u o, CIJ 2
0. Cu (J, CLICj2・2H20, cupric acetate (
CIJ (OAC)2 .R20) etc. can be mentioned as a suitable example, but other copper compounds can rarely be used in this reaction. Between copper catalysts, sodium metal salt of p-chlorophenol is based on 1% i and 0.00
1 to 1.0 times equivalent, preferably o, oos to 0.
It is 10 times equivalent.
ｍ−ジクロロベンゼンの吊はＯ−クロロフェノールのナ
トリウム金属塩を基準にして５〜５０倍当吊であり、大
過剰用いることにより生成した３、４′ −ジクロロフ
ェニルエーテルに更にナトリウム金属塩が反応する二次
反応をおさえることが出来る。反応で用いられるナトリ
ウム金属塩はｍ−ジクロロベンゼン中でｐ−クロロフェ
ノールとナトリ「クム化合物を反応させ、水を系から除
去することにより生成してもよいし、また、芳香族炭化
水素たとえばベンゼン、トルエンなどを溶媒にしてｐ−
クロロフェノールとナトリウム化合物を反応させ、水と
溶媒を除去して生成してもよい。The strength of m-dichlorobenzene is 5 to 50 times higher than that of the sodium metal salt of O-chlorophenol, and when it is used in large excess, the sodium metal salt reacts with the 3,4'-dichlorophenyl ether produced. Secondary reactions can be suppressed. The sodium metal salt used in the reaction may be produced by reacting p-chlorophenol with a sodium cum compound in m-dichlorobenzene and removing water from the system, or may be produced by reacting a sodium cum compound with an aromatic hydrocarbon such as benzene. , p- using toluene etc. as a solvent.
It may also be produced by reacting chlorophenol with a sodium compound and removing water and solvent.
本発明の反応は、カリウム塩を存在せしめることにより
、有利に進行することが多い。The reaction of the present invention often proceeds advantageously in the presence of a potassium salt.
該カリウム塩の種類としては、例えば塩化カリウム、硝
酸カリウム、硫酸カリウム、シュウ酸カリウム、炭酸カ
リウム等があげられ、またクロロフェノールのカリウム
塩を用いることもできる。Examples of the potassium salt include potassium chloride, potassium nitrate, potassium sulfate, potassium oxalate, potassium carbonate, and potassium salt of chlorophenol.
カリウム塩の吊はｐ−フロロフェノールのす１〜リウム
金属塩を基準にして０．０１〜１倍当ｍ、好ましくはＱ
、００５〜０．５倍当ｍが適当である。The amount of potassium salt is 0.01 to 1 times the weight of p-fluorophenol metal salt, preferably Q
, 005 to 0.5 times m is suitable.
反応温度は使用するエーテルの種類などにより若干異な
るが１１０〜２００℃の範囲、好ましくは１４０〜１８
０℃の範囲である。反応時間は反応温度。The reaction temperature varies slightly depending on the type of ether used, but is in the range of 110 to 200°C, preferably 140 to 18°C.
It is in the range of 0°C. The reaction time is the reaction temperature.
媒体の種類などによって左右されるが通常１〜３０時間
の範囲であり好ましくは１〜２０旧間の範囲である。Although it depends on the type of medium, it is usually in the range of 1 to 30 hours, preferably in the range of 1 to 20 hours.
また本発明の反応は不活性ガス中で行なうことが望まし
く、酸素（Ｏｚ）が存在するとタール化合物が生成する
。不活性ガスとしては窒素、アルゴン、ヘリウムなどが
用いられる。Further, the reaction of the present invention is preferably carried out in an inert gas, and if oxygen (Oz) is present, a tar compound will be produced. Nitrogen, argon, helium, etc. are used as the inert gas.
以上、本発明によって高収率で３．４′ −ジクロロジ
フェニルエーテルを得ることが出来るが、これは対応す
るジアミノジフェニルエーテルの製造に導く出発物質と
して用いることが出来、このジアミノ化合物は高分子化
合物の製造に対する原料として楊めて工業的に価値が高
いものである。As described above, 3,4'-dichlorodiphenyl ether can be obtained in high yield according to the present invention, which can be used as a starting material for the production of the corresponding diaminodiphenyl ether, and this diamino compound can be used for the production of polymer compounds. It is of high industrial value as a raw material.
以下実施例を揚げ本発明をさらに詳細に説明する。The present invention will be explained in more detail with reference to Examples below.
実施例１
ｐ−クロロフェノール２５．０ｇ（０，１９５ｍｏｌ）
。Example 1 p-chlorophenol 25.0g (0,195mol)
.
ｍ−ジクロロベンゼン２８４．１ｇ（１，９３３ｍｏｌ
）及び水酸化ナトリウム水溶液（Ｎａ ＯＨＯ，１９５
ｍｏｌ含む）を加熱還流し、系から水を除去した。続い
てジエチレングリコールジエチルエーテル６３．９ｇ（
０，３９４ｍｏｌ）と塩化第一銅０，１９９ （１，９
２ｍｍｏｌ ）とを加え、１５５〜１６０℃で１８時間
加熱撹拌した。反応混合物をろ過して、無機化合物を除
いた後、ろ液を蒸留することにより ３．４′ −ジク
ロロジフェニルエーテル４０．７９ （０，１７０ｍｏ
ｌ＞が得られた。これはｐ−クロロフェノールを基準に
して理論値の８７，２％に対応する。このエーテルのの
沸点（Ｂ、ｐ、）は１１０〜ｂ
であった。m-dichlorobenzene 284.1g (1,933mol
) and aqueous sodium hydroxide solution (Na OHO, 195
mol) was heated to reflux to remove water from the system. Next, 63.9 g of diethylene glycol diethyl ether (
0,394 mol) and cuprous chloride 0,199 (1,9
2 mmol) was added thereto, and the mixture was heated and stirred at 155 to 160°C for 18 hours. After filtering the reaction mixture to remove inorganic compounds, the filtrate was distilled to obtain 3.4'-dichlorodiphenyl ether 40.79 (0,170 mo
l> was obtained. This corresponds to 87.2% of theory, based on p-chlorophenol. The boiling point (B, p,) of this ether was 110-b.
実施例２
ジエチレングリコールジエチルエーテルの代わりに、エ
チレングリコールジブチルエ７テルを同モル吊用いる以
外は実施例１と同様の条件で反応を行った。その結果を
表１に示した。Example 2 A reaction was carried out under the same conditions as in Example 1 except that ethylene glycol dibutyl ether was used in the same molar amount instead of diethylene glycol diethyl ether. The results are shown in Table 1.
比較例１
ジエチレングリコールジエチルエーテルを加えない以外
は実施例１と同様の条件で反応を行った。Comparative Example 1 A reaction was carried out under the same conditions as in Example 1 except that diethylene glycol diethyl ether was not added.
比較例２
塩化第一銅を加えない以外実施例１と同様な条件で反応
を行った。Comparative Example 2 A reaction was carried out under the same conditions as in Example 1 except that cuprous chloride was not added.
また上記比較例１，２の結果を併せて表１に示した。The results of Comparative Examples 1 and 2 are also shown in Table 1.
表１
実施例３．４
ジエチレングリコールジエチルエーテルの代わりにトリ
エチレングリコールジメチルエーテルまたはテトラエチ
レングリコールジメチルエーテルを同モル量用いかつ塩
化カリウム１．４５９を加える以外は実施例１と同様の
条件で反応を行った。Table 1 Example 3.4 A reaction was carried out under the same conditions as in Example 1 except that the same molar amount of triethylene glycol dimethyl ether or tetraethylene glycol dimethyl ether was used instead of diethylene glycol diethyl ether and 1.459 g of potassium chloride was added.
その結果を表２に示した。The results are shown in Table 2.
比較例３〜９
ジエチレングリコールジエチルエーテルの代わりに表２
に記載したエーテル化合物を同モル量用いかつ塩化カリ
ウム１．４５ ｇを加える以外鉱実施例１と同様の条件
で反応を行った。また上記比較例３〜９の結果も併せて
表２に示した。Comparative Examples 3-9 Table 2 instead of diethylene glycol diethyl ether
The reaction was carried out under the same conditions as in Example 1 except that the same molar amount of the ether compound described in Example 1 was used and 1.45 g of potassium chloride was added. The results of Comparative Examples 3 to 9 are also shown in Table 2.
表２
実施例５〜９
塩化第一銅の代わりに表３に記載した銅触媒を用いる以
外は実施例１と同様の条件で反応を行った。その結果を
表３に示した。Table 2 Examples 5 to 9 Reactions were carried out under the same conditions as in Example 1 except that the copper catalyst listed in Table 3 was used instead of cuprous chloride. The results are shown in Table 3.
表３ 代理人弁理士前 １）純 傅−１ ｌ″Ｉ′ ぐ、、’： ’／” ”−、／ 手Ｕごネ「１１正書 １、事イ′１の表示 特願昭 ６１ − １８４２４９ 号２、発明の名称Table 3 Former Patent Attorney 1) Jun Fu-1 l″I′ ingredient,,': '/" ”-,/ Te U Gone “11th book” 1. Display of matter a'1 Patent Application No. 184249 No. 2, Title of the Invention
Claims (1)
クロロベンゼンとを反応条件下で液状を呈する脂肪族グ
リコールのジアルキルエーテル及び銅触媒の存在下反応
せしめることを特徴とする３，４′−ジクロロジフェニ
ルエーテルの製造法。 ２、該反応をカリウム塩の存在下に行なう第１項記載の
製造法。[Claims] 1. A method characterized by reacting a sodium metal salt of p-chlorophenol and m-dichlorobenzene in the presence of a dialkyl ether of an aliphatic glycol that is liquid under the reaction conditions and a copper catalyst. , 4'-Dichlorodiphenyl ether production method. 2. The production method according to item 1, wherein the reaction is carried out in the presence of a potassium salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61184249A JPS6341434A (en) | 1986-08-07 | 1986-08-07 | Production of 3,4'-dichlorodiphenyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61184249A JPS6341434A (en) | 1986-08-07 | 1986-08-07 | Production of 3,4'-dichlorodiphenyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6341434A true JPS6341434A (en) | 1988-02-22 |
| JPH0357093B2 JPH0357093B2 (en) | 1991-08-30 |
Family
ID=16150000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61184249A Granted JPS6341434A (en) | 1986-08-07 | 1986-08-07 | Production of 3,4'-dichlorodiphenyl ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6341434A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115087642A (en) * | 2020-03-10 | 2022-09-20 | 株式会社吴羽 | Preparation method of azole derivative, preparation method of bromohydrin derivative and bromohydrin derivative, and preparation method of 1-chloro-3- (4-chlorophenoxy) benzene |
-
1986
- 1986-08-07 JP JP61184249A patent/JPS6341434A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115087642A (en) * | 2020-03-10 | 2022-09-20 | 株式会社吴羽 | Preparation method of azole derivative, preparation method of bromohydrin derivative and bromohydrin derivative, and preparation method of 1-chloro-3- (4-chlorophenoxy) benzene |
| US11739038B2 (en) | 2020-03-10 | 2023-08-29 | Kureha Corporation | Method for producing azole derivative, bromohydrin derivative and method for producing same, and method for producing 1-chloro-3-(4-chlorophenoxy)benzene |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0357093B2 (en) | 1991-08-30 |
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