JPH0357093B2 - - Google Patents
Info
- Publication number
- JPH0357093B2 JPH0357093B2 JP61184249A JP18424986A JPH0357093B2 JP H0357093 B2 JPH0357093 B2 JP H0357093B2 JP 61184249 A JP61184249 A JP 61184249A JP 18424986 A JP18424986 A JP 18424986A JP H0357093 B2 JPH0357093 B2 JP H0357093B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- ether
- chlorophenol
- salt
- carried out
- 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.)
- Expired - Lifetime
Links
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000010949 copper Substances 0.000 claims description 12
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 7
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 5
- 150000001983 dialkylethers Chemical class 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 5
- 150000001555 benzenes Chemical class 0.000 description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 5
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 5
- 150000002170 ethers Chemical class 0.000 description 5
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 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 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000001879 copper Chemical class 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
- -1 methylene, ethylene, propylene Chemical group 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 150000003388 sodium compounds Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 2
- 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 150000001447 alkali salts Chemical class 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
- 239000011261 inert gas Substances 0.000 description 2
- 238000000034 method Methods 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
- 230000021148 sequestering of metal ion Effects 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
- WXEOWWVZWWGBBQ-UHFFFAOYSA-N 1,2-dichloro-3-(2,3-dichlorophenoxy)benzene Chemical compound ClC1=CC=CC(OC=2C(=C(Cl)C=CC=2)Cl)=C1Cl WXEOWWVZWWGBBQ-UHFFFAOYSA-N 0.000 description 1
- 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
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 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
- 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000004707 phenolate Chemical class 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
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
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３，4′−ジアミノ
ジフエニルエーテルの中間体と成り得る３，4′−
ジクロロジフエニルエーテルの製造法に関するも
のである。
従来技術
従来、ジフエニルエーテル類の合成法としてフ
エノールとハロゲン化ベンゼンをアルカリ塩存在
下反応させるウイリアムソン（Williamson）反
応が知られている。この反応を極性溶媒中行なう
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殆ほとんど得られない。
一方、フエ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（Ullmann）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
エ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エ
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も出来ないと考えられる。そ
こで、クロロフエ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号公報）も
あるが、ジフエニルエーテルの収率はかならずし
も高くない。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る例
（特開昭56−29539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。
本発明者らは種々の研究の結果、ｐ−クロロフ
エ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
反応せしめると極めて高収率で３，4′−ジクロロ
ジフエニルエーテルが得られることを見い出し本
発明に至つた。
発明の構成
本発明はｐ−クロロフエ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
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させることを特徴とする
３，4′−ジクロロフエニルエーテルの製造法であ
る。
本発明の方法に使用される前記エーテルとして
は種々のものが使用出来る。
その例としては、一般式R1［Ｏ−Ｒ］nO−
R2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。
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トラエチ
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′−ジクロロジフエニルエーテルを高
収率で得ることはできない。
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−クロロフエノールのナトリウム金属
塩に対して0.5〜20倍当量の範囲で十分良好な結
果が得られるが好ましくは１〜５倍当量の範囲で
ある。反応に用いられる銅触媒としては、金属銅
（Cu），CuO，Cu2Ｏ，CuCl，CuCl2・2H2Ｏ，酢
酸第二銅（Cu（OAc）2・H2Ｏ）等を好適な例とし
てあげられるが、その他の銅化合物であつてもこ
の反応に用いることが出来る。銅触媒の量はｐ−
クロロフエノールのナトリウム金属塩を基準とに
して0.001〜1.0倍当量であり、好ましくは0.005〜
0.10倍当量である。
ｍ−ジクロロベンゼンの量はｐ−クロロフエノ
ールのナトリウム金属塩を基準にして５〜50倍当
量であり、大過剰用いることにより生成した３，
4′−ジクロロフエ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−クロロフエノールとナト
リウ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−クロロフエノールとナトリウム化合物を反応
させ、水を溶媒を除去して生成してもよい。
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。
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，シユウ酸カ
リウム，炭酸カリウム等があげられ、またクロロ
フエノールのカリウム塩を用いることもできる。
カリウム塩の量はｐ−フロロフエノールのナト
リウム金属塩を基準にして、0.01〜１倍当量、好
ましくは0.005〜0.5倍当量が適当である。
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
〜180℃の範囲である。反応時間は反応温度、媒
体の種類などによつ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時間の範囲であ
る。
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（O2）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。
以上、本発明によつて高収率で３，4′−ジクロ
ロジフエ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エ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
として極めて工業的に価値が高いものである。
以下実施例を揚げ本発明をさらに詳細に説明す
る。
実施例 １
ｐ−クロロフエノール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（NaOH0.195mol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0.19g（1.92mmol）とを
加え、155〜160℃で18時間加熱攪拌した。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′−ジクロロフエニルエ
ーテル40.7g（0.170mol）が得られた。これはｐ−
クロロフエノールを基準にして理論値の87.2％に
対応する。このエーテルの沸点（B.p.）は110〜
112℃／0.45mmHgであつた。
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ーテルを同
モル量用いる以外は実施例１と同様の条件で反応
を行つた。その結果を表１に示した。
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つ
た。
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
件で反応を行つた。
また上記比較例１，２の結果を併せて表１に示
した。
Industrial Application Fields The present invention is directed to 3,4'-diaminodiphenyl ether, which can be used as an intermediate for 3,4'-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. Prior 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. If this reaction is carried out in a polar solvent, the reaction temperature can be lowered, but the reaction progresses easily only in the case of activated halogenated benzene. Almost no gain. On the other hand, the Ullmann reaction is also 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. 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 phenolates nor convert copper salts into reactive forms. Therefore, there is an example (Japanese Unexamined Patent Publication No. 49-62434) in which the reaction is carried out by adding an excess of chlorophenol as a solvent, but the yield of diphenyl ether is not always high. Furthermore, there is an example (JP-A-56-29539) in which a metal ion sequestering agent is added to the reaction with inert halogenated benzene, but this requires the use of an expensive metal ion sequestering agent. As a result of various studies, the present inventors have found that when the sodium salt of p-chlorophenol and m-dichlorobenzene are reacted in the presence of dialkyl ether of aliphatic glycol, which is liquid under reaction conditions in the presence of a copper catalyst, extremely high It was discovered that 3,4'-dichlorodiphenyl ether can be obtained in high yield, leading to the present invention. Structure of the Invention The present invention is characterized in that the sodium salt of p-chlorophenol and m-dichlorobenzene are reacted in the presence of a dialkyl ether of an aliphatic glycol that is liquid under the reaction conditions and a copper catalyst. - A method for producing dichlorophenyl ether. Various ethers can be used as the ether used in the method of the present invention. An example is the general formula R 1 [O-R]nO-
Ethers represented by R 2 are preferred. Here R
is alkylene having 1 to 4 carbon atoms such as methylene, ethylene, propylene, and butylene, preferably ethylene or propylene. Also with R 1
R 2 are the same or different and represent a lower alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 or more. Specific examples of dialkyl ethers of aliphatic glycols 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 preferred. 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. These ethers can be used alone or in combination of two or more. The amount of these ethers to be used is preferably in the range of 0.5 to 20 times the equivalent of the sodium metal salt of p-chlorophenol to obtain good results, but preferably in the range of 1 to 5 times the equivalent. Preferred examples of copper catalysts used in the reaction include metallic copper (Cu), CuO, Cu 2 O, CuCl, CuCl 2 2H 2 O, cupric acetate (Cu(OAc) 2 2H 2 O), etc. However, other copper compounds can also be used in this reaction. The amount of copper catalyst is p-
Based on the sodium metal salt of chlorophenol, it is 0.001 to 1.0 times equivalent, preferably 0.005 to 1.0 times equivalent.
It is 0.10 times equivalent. The amount of m-dichlorobenzene is 5 to 50 times equivalent based on the sodium metal salt of p-chlorophenol.
It is possible to suppress the secondary reaction in which 4'-dichlorophenyl ether reacts with sodium metal salt. The sodium metal salt used in the reaction may be produced by reacting p-chlorophenol with a sodium compound in m-dichlorobenzene and removing water from the system, or may be produced by reacting p-chlorophenol with a sodium compound in m-dichlorobenzene and removing water from the system. Alternatively, p-chlorophenol and a sodium compound may be reacted using a solvent such as the like, and water may be produced by removing the solvent. The reaction of the present invention often proceeds advantageously in the presence of a potassium salt. Examples of the potassium salt include potassium chloride, potassium nitrate, potassium sulfate, potassium oxalate, potassium carbonate, and potassium salt of chlorophenol. The amount of potassium salt is suitably 0.01 to 1 equivalent, preferably 0.005 to 0.5 equivalent, based on the sodium metal salt of p-fluorophenol. The reaction temperature varies slightly depending on the type of ether used, but is in the range of 110 to 200°C, preferably 140°C.
~180℃ range. The reaction time depends on the reaction temperature, type of medium, etc., but is usually in the range of 1 to 30 hours, preferably in the range of 1 to 20 hours. Further, the reaction of the present invention is preferably carried out in an inert gas, and if oxygen (O 2 ) is present, a tar compound will be produced. Nitrogen, argon, helium, etc. are used as the inert gas. As described above, according to the present invention, 3,4'-dichlorodiphenyl ether can be obtained in high yield, which can be used as a starting material for the production of the corresponding diaminodiphenyl ether, and this diamino compound is of extremely high industrial value as a raw material for the production of polymer compounds. The present invention will be explained in more detail with reference to Examples below. Example 1 p-chlorophenol 25.0g (0.195mol), m-
284.1 g (1.933 mol) of dichlorobenzene and an aqueous sodium hydroxide solution (containing 0.195 mol of NaOH) were heated to reflux to remove water from the system. Next, 63.9g of diethylene glycol diethyl ether
(0.394 mol) and 0.19 g (1.92 mmol) of cuprous chloride were added, 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 40.7 g (0.170 mol) of 3,4'-dichlorophenyl ether. This is p-
Corresponds to 87.2% of the theoretical value based on chlorophenol. The boiling point (Bp) of this ether is 110~
The temperature was 112℃/0.45mmHg. 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. 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. Comparative Example 2 A reaction was carried out under the same conditions as in Example 1 except that cuprous chloride was not added. The results of Comparative Examples 1 and 2 are also shown in Table 1.
【表】
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1.45gを加える
以外は実施例１と同様の条件で反応を行つた。そ
の結果を表２に示した。
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1.45gを加える以外は実施例
１と同様の条件で反応を行つた。また上記比較例
３〜９の結果も併せて表２に示した。[Table] Examples 3 and 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 1.45 g of potassium chloride was added. The results are shown in Table 2. Comparative Examples 3 to 9 A reaction was carried out under the same conditions as in Example 1, except that the same molar amount of the ether compound shown in Table 2 was used instead of diethylene glycol diethyl ether and 1.45 g of potassium chloride was added. The results of Comparative Examples 3 to 9 are also shown in Table 2.
【表】【table】
【表】
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つ
た。その結果を表３に示した。[Table] 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.
Claims (1)
ｍ−ジ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′−ジクロロジフエ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 sodium metal salt of p-chlorophenol and m-dichlorobenzene are reacted in the presence of a dialkyl ether of an aliphatic glycol that is liquid under the reaction conditions and a copper catalyst. 3. Method for producing 4'-dichlorodiphenyl ether. 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 JPS6341434A (en) | 1988-02-22 |
| JPH0357093B2 true 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) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021182530A1 (en) | 2020-03-10 | 2021-09-16 | 株式会社クレハ | Method for producing azole derivative, bromohydrin derivative and method for producing same, and method for producing 1-chloro-3-(4-chlorophenoxy)benzene |
-
1986
- 1986-08-07 JP JP61184249A patent/JPS6341434A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6341434A (en) | 1988-02-22 |
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