JPH01160935A - Production of 4-biphenyl p-tolyl ether - Google Patents
Production of 4-biphenyl p-tolyl etherInfo
- Publication number
- JPH01160935A JPH01160935A JP62319384A JP31938487A JPH01160935A JP H01160935 A JPH01160935 A JP H01160935A JP 62319384 A JP62319384 A JP 62319384A JP 31938487 A JP31938487 A JP 31938487A JP H01160935 A JPH01160935 A JP H01160935A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- reaction
- phenylphenol
- biphenyl
- catalyst
- 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
- -1 4-biphenyl p-tolyl ether Chemical compound 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 8
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 34
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 abstract description 8
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 abstract description 6
- 239000005749 Copper compound Substances 0.000 abstract description 5
- 150000001880 copper compounds Chemical class 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 abstract description 3
- 150000001879 copper Chemical class 0.000 abstract description 2
- 229940116318 copper carbonate Drugs 0.000 abstract description 2
- 150000004699 copper complex Chemical class 0.000 abstract description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 abstract description 2
- 239000005725 8-Hydroxyquinoline Substances 0.000 abstract 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 229960003540 oxyquinoline Drugs 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 7
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 235000011181 potassium carbonates Nutrition 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000006887 Ullmann reaction Methods 0.000 description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 3
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 150000001987 diarylethers Chemical class 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- OKVJCVWFVRATSG-UHFFFAOYSA-N 3-hydroxybenzyl alcohol Chemical compound OCC1=CC=CC(O)=C1 OKVJCVWFVRATSG-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、感熱記録材における増感剤として有用である
４−ビフェニルｐ−）リルエーテルの製造法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing 4-biphenyl p-)lyl ether, which is useful as a sensitizer in heat-sensitive recording materials.
〔従来の技術・解決しようとする問題点〕ジアリールエ
ーテル類の製造法としては、アリールオキシ金属塩とハ
ロゲン化アリールを銅触媒の存在下で反応させるいわゆ
るウルマン（Ｕｌｍａｎｎ）反応が広く知られている。[Prior art/Problems to be solved] As a method for producing diaryl ethers, the so-called Ulmann reaction, in which an aryloxy metal salt and an aryl halide are reacted in the presence of a copper catalyst, is widely known. .
このウルマン反応において他の条件が同しであれば、臭
素化子り−ルに比較して塩素化アリールの反応性は著し
く低下することが知られているが、その反面、極めて安
価であり工業的には塩素化アリールを出発原料とするこ
とが望ましい。It is known that in this Ullmann reaction, if other conditions are the same, the reactivity of chlorinated aryl is significantly lower than that of brominated aryl, but on the other hand, it is extremely cheap and industrially In particular, it is desirable to use a chlorinated aryl as a starting material.
４−ビフェニルｐ−）リルエーテルの製造法においても
出発原料にｐ−クロロトルエンを用いる方法が研究され
ており、特公昭５６−４５１号公報には、ｐ−フェニル
フェノールとｐ−クロロトルエンから４−ビフェニルｐ
−トリルエーテルを製造する方法において、複数の無機
銅化合物を触媒とし、ジメチルアセトアミドを反応促進
剤として用いることが開示されている。しかしながら、
この方法は反応時間が長く収率も到底工業的に満足でき
るものではない。A method for producing 4-biphenyl p-)lyl ether using p-chlorotoluene as a starting material has also been studied, and Japanese Patent Publication No. 1983-451 describes the production of 4-biphenylphenol and p-chlorotoluene from p-phenylphenol and p-chlorotoluene. biphenyl p
- In a method for producing tolyl ether, it is disclosed that a plurality of inorganic copper compounds are used as a catalyst and dimethylacetamide is used as a reaction accelerator. however,
This method takes a long reaction time and the yield is not industrially satisfactory.
また、一般にウルマン反応において塩素化アリールを出
発原料とする場合、その反応を促進させるためＮ、Ｎ−
ジメチルホルムアミド、Ｎ−メチルピロリドン、ジメチ
ルスルホキシド、ヘキサメチルホスホルアミドなどの極
性非水溶媒類やジエチレングリコールアルキルエーテル
などのポリエーテル類を用いることが知られているが、
４−ビフェニルｐ−）リルエーテルの製造に当たって、
これらの極性非水溶媒類やポリエーテル類を用いても工
業的に充分な収量を得ることができなかった。In general, when a chlorinated aryl is used as a starting material in the Ullmann reaction, N, N-
It is known to use polar nonaqueous solvents such as dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, and hexamethylphosphoramide, and polyethers such as diethylene glycol alkyl ether.
In producing 4-biphenyl p-)lyl ether,
Even when these polar non-aqueous solvents and polyethers were used, industrially sufficient yields could not be obtained.
ところで、特開昭６１−２５７９３８号公報には銅化合
物触媒及び塩基の存在下、クロロベンゼンとｍ−ヒドロ
キシベンジルアルコールとの反応によりｍ−フェノキシ
ヘンシルアルコールを製造する方法において、Ｎ、 Ｎ
’ −ジメチルイミダゾリジノンを含むクロロベンゼ
ンより高沸点の極性溶媒中で反応させることが開示さて
いるが、これらのＮ、 Ｎ’ −ジメチルイミダゾ
リジノンの使用は溶媒としての使用であって、しかも原
料であるクロロベンゼンと特定の比率を正しく選び、適
切な温度範囲で生成水をクロロベンゼンと共沸させて系
外に水を除去しながら行なうというもので、厳格な条件
のもとでのみ収率を向上させるものである。それゆえに
、同じウルマン反応であっても、このように複雑な反応
条件を原料化合物の異なる反応に応用することは困難で
あり、さらにＮ、 Ｎ’−ジメチルイミダゾリジノン自
身も溶媒としてはかなり高価なものである。By the way, JP-A-61-257938 discloses a method for producing m-phenoxyhensyl alcohol by reacting chlorobenzene and m-hydroxybenzyl alcohol in the presence of a copper compound catalyst and a base, in which N, N
Although it is disclosed that the reaction is carried out in a polar solvent with a boiling point higher than that of chlorobenzene containing '-dimethylimidazolidinone, the use of these N,N'-dimethylimidazolidinones is only for use as a solvent, and moreover, The method involves selecting a specific ratio of chlorobenzene and azeotropically producing water with chlorobenzene in an appropriate temperature range to remove water from the system. Yields can only be improved under strict conditions. It is something that makes you Therefore, even for the same Ullmann reaction, it is difficult to apply such complicated reaction conditions to different reactions of starting compounds, and N,N'-dimethylimidazolidinone itself is quite expensive as a solvent. It is something.
このような状況のもとで感熱記録材における増感剤とし
て極めて有用である４−ビフェニルｐ−トリルエーテル
の簡便で経済的しかも工業的に有利な製造方法の開発が
希求されていた。Under these circumstances, there has been a desire to develop a simple, economical, and industrially advantageous manufacturing method for 4-biphenyl p-tolyl ether, which is extremely useful as a sensitizer in heat-sensitive recording materials.
本発明者らは、これらの状況のもとで鋭意研究を重ねた
結果、４−ビフェニルｐ−４リルエーテルの製造法にお
いて反応促進剤として１，３−ジメチル−２−イミダゾ
リジノンを用いることによって顕著に収率が向上するこ
とを見出し、本発明を完成するに至った。As a result of extensive research under these circumstances, the present inventors found that by using 1,3-dimethyl-2-imidazolidinone as a reaction accelerator in the method for producing 4-biphenyl p-4yl ether, It was discovered that the yield was significantly improved, and the present invention was completed.
すなわち、本発明はｐ−フェニルフェノールとｐ−クロ
ロトルエンとを銅触媒の存在下、反応促進剤として１．
３−ジメチル−２−イミダゾリジノンを用いて反応させ
ることを特徴とする４−ビフェニルｐ−１リルエーテル
の製造法に関する。That is, in the present invention, p-phenylphenol and p-chlorotoluene are used as reaction accelerators in the presence of a copper catalyst.
The present invention relates to a method for producing 4-biphenyl p-1yl ether, which is characterized by carrying out the reaction using 3-dimethyl-2-imidazolidinone.
本発明をさらに詳細に説明すると、使用される１、３−
ジメチル−２−イミダゾリジノンは、ｐ−フェニルフェ
ノールに対し約１〜約３（ｌｆｆｉ％程度である。To explain the present invention in more detail, the 1,3-
Dimethyl-2-imidazolidinone is about 1 to about 3 (lffi%) relative to p-phenylphenol.
銅触媒としては、触媒能を有するものならばいずれでも
よく、たとえば銅粉末や塩化銅、炭酸銅などの無機銅化
合物、有機カルボン酸の銅塩などが使用できるが、特に
８−オキシキノリンまたはアセチルアセトンの銅錯体触
媒が好ましい。これらの錯体は錯体として別途調製した
ものを使用してもよいが、８−オキシキノリンやアセチ
ルアセトンなどと塩化銅のごとき無機銅化合物を別個に
反応器中に入れ、その中で錯塩を形成させてもよい。銅
触媒の使用量は反応温度、反応時間により異なるが、通
常ｐ−フェニルフェノールに対し０．０１〜１０重量％
、好ましくは０．１〜３．０重量％程度が使用される。As the copper catalyst, any catalyst may be used as long as it has catalytic ability, such as copper powder, inorganic copper compounds such as copper chloride and copper carbonate, and copper salts of organic carboxylic acids, but in particular, 8-oxyquinoline or acetylacetone can be used. copper complex catalysts are preferred. These complexes may be prepared separately as complexes, but 8-oxyquinoline, acetylacetone, etc. and an inorganic copper compound such as copper chloride may be separately placed in a reactor and a complex salt formed therein. Good too. The amount of copper catalyst used varies depending on the reaction temperature and reaction time, but is usually 0.01 to 10% by weight based on p-phenylphenol.
, preferably about 0.1 to 3.0% by weight.
原料として使用されるｐ−フェニルフェノールは、その
アルカリ金属塩としても使用でき、ｐ−フェニルフェノ
ールとアルカリ金属アルコラード（カリウムアルコラー
ド、ナトリウムアルコラードなど）、水酸化アルカリ
（水酸化カリウム、水酸化ナトリウムなど）、炭酸アル
カリ （炭酸カリウム、炭酸ナトリウムなど）、重炭酸
アルカリ （重炭酸カリウム、重炭酸ナトリウムなど）
などとの反応により得られるが、アルカリ金属塩を単離
したのち反応に使用する必要はなく、ｐ−フェニルフェ
ノールと水酸化アルカリ、炭酸アルカリ、重炭酸アルカ
リなどを同−反応器中に仕込み、その反応器中でｐ−フ
ェニルフェノールのアルカリ金属塩を生成させればよい
。アルカリはｐ−フェニルフェノール１モルに対して０
．９〜２．０アルカリ当量、好ましくは０．９５〜１．
５アルカリ当量を使用スる。また、ｐ−クロロトルエン
はトルエン、キシレンのごとき不活性溶剤を反応溶媒と
して使用スる場合、ｐ−フェニルフェノール１モルに対
して１．０〜１．５モル倍使用すればよいが、ｐ−クロ
ロトルエン自体を反応溶媒とする場合であればさらに過
剰の量を使用できる。p-phenylphenol used as a raw material can also be used as its alkali metal salt, and p-phenylphenol and alkali metal alcoholade (potassium alcoholade, sodium alcoholade, etc.), alkali hydroxide
(potassium hydroxide, sodium hydroxide, etc.), alkali carbonate (potassium carbonate, sodium carbonate, etc.), alkali bicarbonate (potassium bicarbonate, sodium bicarbonate, etc.)
However, it is not necessary to isolate the alkali metal salt and use it in the reaction; instead, p-phenylphenol and alkali hydroxide, alkali carbonate, alkali bicarbonate, etc. are charged into the same reactor. An alkali metal salt of p-phenylphenol may be produced in the reactor. Alkali is 0 per mole of p-phenylphenol.
．． 9-2.0 alkali equivalent, preferably 0.95-1.
5 alkali equivalents are used. In addition, when using an inert solvent such as toluene or xylene as a reaction solvent, p-chlorotoluene may be used in an amount of 1.0 to 1.5 moles per mole of p-phenylphenol. If chlorotoluene itself is used as a reaction solvent, an even larger amount can be used.
反応は１２０〜２８０℃、好ましくは常圧下１４０〜２
００℃で５〜２０時間加熱攪拌する。ｐ−フェニルフェ
ノールとアルカリを仕込み反応器内でｐ−フェニルフェ
ノールのアルカリ塩を形成させる場合には反応系内に水
が生成してくるが、始めに触媒を除く他の反応試剤を仕
込み加熱還流により共沸してくる水分を系外に除去した
のち触媒を加え反応を開始してもよい。また、触媒を含
む全ての反応試剤を仕込んだのち加熱還流し、共沸して
くる水分を系外に取り出しながら反応を進めてもよい。The reaction is carried out at 120-280°C, preferably at 140-280°C under normal pressure.
Heat and stir at 00°C for 5 to 20 hours. When p-phenylphenol and an alkali are charged to form an alkali salt of p-phenylphenol in a reactor, water is generated in the reaction system, but first the other reaction reagents except the catalyst are charged and heated under reflux. The reaction may be started by adding a catalyst after removing water azeotropically from the system. Alternatively, the reaction may proceed while heating and refluxing all the reaction reagents including the catalyst and removing azeotropic water from the system.
反応終了後、水洗、溶媒留去、蒸留、再結晶など通常の
操作を加えることにより高純度の目的物が得られる。After the reaction is completed, a highly pure target product can be obtained by performing usual operations such as washing with water, distilling off the solvent, distillation, and recrystallization.
以下、実施例により本発明をより具体的に説明するが、
本発明はこれらの実施例により何ら限定されるものでは
ない。Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited in any way by these Examples.
実施例１
温度計、撹拌棒、還流分水器を付した４つロフラスコに
ｐ−フェニルフェノール５５４．７ｇ（３，２０モル）
、ｐ−クロロトルエン６０７．７ｇ（４，８０モル）、
炭酸カリウム２６５．４ ｇ （１，９２モル）、８−
オキシキノリン銅錯体８．Ｏｇおよび１．３−ジメチル
−２−イミダゾリジノン８２ｇを入れ、窒素雰囲気下で
徐々に温度を上げながら１４０〜１８０℃で５時間攪拌
し、還流により分水器中に分離してきた水は適宜系外に
除去した。Example 1 554.7 g (3.20 mol) of p-phenylphenol was placed in a four-loaf flask equipped with a thermometer, stirring bar, and reflux separator.
, p-chlorotoluene 607.7g (4.80 mol),
Potassium carbonate 265.4 g (1,92 mol), 8-
Oxyquinoline copper complex8. Add Og and 82 g of 1,3-dimethyl-2-imidazolidinone and stir at 140 to 180°C for 5 hours while gradually increasing the temperature under a nitrogen atmosphere. Removed from the system.
さらに１７０〜１８５°Ｃで１５時間加熱撹拌したのち
反応物中のｐ−フェニルフェノールとｐ−ビフェニルｐ
−１−リルエーテルの存在比をＧＬＣ（ｇａｓ−１ｉｑ
ｕｉｄ ｃｈｒｏｍａｔｏｇｒａｐｈｙ）面積比にて分
析すると１．５対９８．５であった。反応終了後、ｌＱ
ｍｍＨｇの減圧下に反応物を濃縮するとｐ−クロロトル
エンと１．３−ジメチル−２−イミダゾリジノンからな
る留出物２７０ｇが得られた。濃縮残金にトルエン４０
０ｍ１を加え、反応物を溶解し有機層を１０％水酸化ナ
トリウム水、１０％硫酸水、水で順次洗浄したのちトル
エンを減圧下に留去すると淡褐色の４−ビフェニルｐ−
トリルエーテルの粗生成物７９６ｇが得られた（粗収率
９５％）。さらに粗生成物を２ｍｍ１１ｇの減圧下に蒸
留すると留温１９０〜１９５℃で、融点９７〜９９℃の
白色の目的物７７５ｇが得られた（収率９２％）。After further heating and stirring at 170 to 185°C for 15 hours, p-phenylphenol and p-biphenyl p in the reaction product were mixed.
The abundance ratio of -1-lyl ether was determined by GLC (gas-1iq
When analyzed by area ratio (UID chromatography), it was 1.5:98.5. After the reaction is complete, lQ
The reaction product was concentrated under reduced pressure of mmHg to obtain 270 g of a distillate consisting of p-chlorotoluene and 1,3-dimethyl-2-imidazolidinone. Add 40% toluene to the concentrated residue
0 ml was added, the reactants were dissolved, and the organic layer was sequentially washed with 10% sodium hydroxide solution, 10% sulfuric acid solution, and water, and the toluene was distilled off under reduced pressure to obtain light brown 4-biphenyl p-
796 g of crude tolyl ether was obtained (crude yield 95%). Further, the crude product was distilled to 2 mm and 11 g under reduced pressure to obtain 775 g of a white target product with a distillation temperature of 190 to 195°C and a melting point of 97 to 99°C (yield: 92%).
実施例２
ｐ−フェニルフェノール３４０ｇ（２，０モル）、ｐ−
クロロトルエン６３０ｇ（５，０モル） 、Ｌ３−ジメ
チル−２−イミダゾリジノン６８ｇおよび水酸化ナトリ
ウム８１．０ｇ（２，０モル）を混合し１６０〜１６８
℃で加熱攪拌し、共沸還流により分離してくる水分を系
外に除去したのち、８−オキシキノリン銅錯体を５．０
ｇ加え１５５〜１６５℃で１５時間加熱攪拌を続けた。Example 2 340 g (2.0 mol) p-phenylphenol, p-
630 g (5.0 mol) of chlorotoluene, 68 g of L3-dimethyl-2-imidazolidinone and 81.0 g (2.0 mol) of sodium hydroxide were mixed to form a mixture of 160 to 168 g.
After heating and stirring at ℃ and removing water separated from the system by azeotropic reflux, the 8-oxyquinoline copper complex was reduced to 5.0
g was added, and heating and stirring was continued at 155 to 165°C for 15 hours.
Ｇ Ｌ Ｃ分析によればｐ−フェニルフェノールの目的
物への転化率は９８．０％であった。反応終了後、実施
例１と同様に処理し、粗生成物４９０ｇを得た（粗収率
９４％）。粗生成物をイソプロピルアルコールに溶解し
、活性炭および白土で脱色したのち再結晶すると、目的
物として融点９７〜９８℃の白色の結晶が得られた。According to GLC analysis, the conversion rate of p-phenylphenol to the target product was 98.0%. After the reaction was completed, it was treated in the same manner as in Example 1 to obtain 490 g of a crude product (crude yield 94%). The crude product was dissolved in isopropyl alcohol, decolorized with activated carbon and clay, and then recrystallized to obtain white crystals with a melting point of 97 to 98°C as the desired product.
実施例３
ｐ−フェニルフェノール３４．０ｇ（０，２モル）、ｐ
−クロロトルエン５０．６ｇ（０，４モル）、炭酸カリ
ウム１６．６ｇ（０，１２モル）、１．３−ジメチル−
２−イミダゾリジノン６．８ｇおよびアセチルアセトン
銅錯体０．５ｇを混合し１４０〜１８０°Ｃで４時間撹
拌した後、還流により分水器中に分離してきた水を系外
に除去し、さらに１７０〜１８５℃で１５時間撹拌した
。ＧＬＣ分析によればｐ−フェニルフェノールの目的物
への転化率は９５．２％であった。Example 3 34.0 g (0.2 mol) p-phenylphenol, p-phenylphenol
-chlorotoluene 50.6 g (0.4 mol), potassium carbonate 16.6 g (0.12 mol), 1.3-dimethyl-
After mixing 6.8 g of 2-imidazolidinone and 0.5 g of acetylacetone copper complex and stirring at 140 to 180°C for 4 hours, the water separated in the water separator by reflux was removed from the system, and further 170 g of acetylacetone copper complex was mixed. Stir at ˜185° C. for 15 hours. According to GLC analysis, the conversion rate of p-phenylphenol to the target product was 95.2%.
実施例４
実施例３において、アセチルアセトン銅錯体を塩化第一
＆Ｍ１．５ｇに代えて実施例３と同様にして水を除去し
たのち、１８０〜２２０℃で２０時間反応すると転化率
は９３．２％であった。Example 4 In Example 3, the acetylacetone copper complex was replaced with 1.5 g of Daiichi &M chloride, water was removed in the same manner as in Example 3, and the reaction was performed at 180 to 220°C for 20 hours, resulting in a conversion rate of 93.2%. Met.
比較例１
ｐ−フェニルフェノール３４．０ｇ（０，２モル）、ｐ
−クロロトルエン５０．６ｇ（０，４モル）、炭酸カリ
ウム１６．６ｇ（０，１２モル）、８−オキシキノリン
銅錯体０．５ｇおよびジメチルスルホキシド１７ｇを混
合し加熱還流により分離してきた水を除去した後、１７
０〜１８５℃で２０時間反応した。この場合の転化率は
８４．２％であった。Comparative example 1 p-phenylphenol 34.0 g (0.2 mol), p
- Mix 50.6 g (0.4 mol) of chlorotoluene, 16.6 g (0.12 mol) of potassium carbonate, 0.5 g of 8-oxyquinoline copper complex, and 17 g of dimethyl sulfoxide and remove the separated water by heating under reflux. After that, 17
The reaction was carried out at 0 to 185°C for 20 hours. The conversion rate in this case was 84.2%.
比較例２
比較例１において、ジメチルスルホキシドをジエチレン
グリコールジブチルエーテル１７ｇに代え、比較例１と
同様に反応した。この場合の転化率は７８．５％であっ
た。Comparative Example 2 In Comparative Example 1, dimethyl sulfoxide was replaced with 17 g of diethylene glycol dibutyl ether, and the reaction was carried out in the same manner as in Comparative Example 1. The conversion rate in this case was 78.5%.
比較例３
比較例１において、ジメチルスルホキシドを添加しない
他は比較例１と同様に反応した。この場合の転化率は７
４．６％であった。Comparative Example 3 In Comparative Example 1, the reaction was carried out in the same manner as in Comparative Example 1 except that dimethyl sulfoxide was not added. The conversion rate in this case is 7
It was 4.6%.
感熱記録材の増感剤として有用な４−ビフェニルｐ−）
リルエーテルを製造するに当たり、特定のジアリールエ
ーテルの製造に厳格な条件のもとで、溶媒として使用で
きることしか認識されていなかった１、３−ジメチル−
２−イミダゾリジノを
ンが反応促進剤として使用することにより、上述の実施
例および比較例を含む明細書の記載から明らかなように
、従来の製法に比べて目的物を低い反応温度、短い反応
時間、高い収率で得ることができるとともに、従来の１
．３−ジメチル−２−イミダゾリジノンのジアリールエ
ーテル反応への利用方法に比べ、非常に筒便な操作で本
発明の目的物を得られるという利点を有する。4-biphenyl p-) useful as a sensitizer for heat-sensitive recording materials
In producing lylether, it was only recognized that 1,3-dimethyl- could be used as a solvent under strict conditions for producing specific diaryl ethers.
By using 2-imidazolidino as a reaction accelerator, it is possible to produce the desired product at a lower reaction temperature and in a shorter reaction time than with conventional production methods, as is clear from the description of the specification including the above-mentioned Examples and Comparative Examples. , can be obtained in high yield and at the same time as conventional 1
．． Compared to the method of using 3-dimethyl-2-imidazolidinone for diaryl ether reaction, this method has the advantage that the object of the present invention can be obtained with a very convenient operation.
Claims (1)
媒の存在下、反応促進剤として１，３−ジメチル−２−
イミダゾリジノンを用いて反応させることを特徴とする
４−ビフェニルｐ−トリルエーテルの製造法。p-phenylphenol and p-chlorotoluene were reacted in the presence of a copper catalyst with 1,3-dimethyl-2-
A method for producing 4-biphenyl p-tolyl ether, which comprises reacting with imidazolidinone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62319384A JPH01160935A (en) | 1987-12-16 | 1987-12-16 | Production of 4-biphenyl p-tolyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62319384A JPH01160935A (en) | 1987-12-16 | 1987-12-16 | Production of 4-biphenyl p-tolyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01160935A true JPH01160935A (en) | 1989-06-23 |
| JPH0541616B2 JPH0541616B2 (en) | 1993-06-24 |
Family
ID=18109557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62319384A Granted JPH01160935A (en) | 1987-12-16 | 1987-12-16 | Production of 4-biphenyl p-tolyl ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01160935A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4982010A (en) * | 1989-10-31 | 1991-01-01 | Yoshitomi Pharmaceutical Industries, Ltd. | Method of producing 4-biphenyl p-tolyl ether |
| JPH03148235A (en) * | 1989-11-01 | 1991-06-25 | Yoshitomi Pharmaceut Ind Ltd | Preparation of 4-biphenyl-p-tolyl ether |
| JP2009132713A (en) * | 2007-11-30 | 2009-06-18 | Saltigo Gmbh | Improved method for catalytic synthesis of diaryl ether |
-
1987
- 1987-12-16 JP JP62319384A patent/JPH01160935A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4982010A (en) * | 1989-10-31 | 1991-01-01 | Yoshitomi Pharmaceutical Industries, Ltd. | Method of producing 4-biphenyl p-tolyl ether |
| JPH03148235A (en) * | 1989-11-01 | 1991-06-25 | Yoshitomi Pharmaceut Ind Ltd | Preparation of 4-biphenyl-p-tolyl ether |
| JP2009132713A (en) * | 2007-11-30 | 2009-06-18 | Saltigo Gmbh | Improved method for catalytic synthesis of diaryl ether |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0541616B2 (en) | 1993-06-24 |
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