JPH10139699A - Method for producing 4,4'-bischloromethylbiphenyl - Google Patents
Method for producing 4,4'-bischloromethylbiphenylInfo
- Publication number
- JPH10139699A JPH10139699A JP29642196A JP29642196A JPH10139699A JP H10139699 A JPH10139699 A JP H10139699A JP 29642196 A JP29642196 A JP 29642196A JP 29642196 A JP29642196 A JP 29642196A JP H10139699 A JPH10139699 A JP H10139699A
- Authority
- JP
- Japan
- Prior art keywords
- bischloromethylbiphenyl
- reaction
- producing
- thionyl chloride
- chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical group C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 48
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 30
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 18
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000004305 biphenyl Substances 0.000 claims abstract description 15
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 9
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 9
- 239000011592 zinc chloride Substances 0.000 claims abstract description 9
- 239000012320 chlorinating reagent Substances 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 19
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 19
- 239000007789 gas Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 229930040373 Paraformaldehyde Natural products 0.000 description 7
- 229920002866 paraformaldehyde Polymers 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RAZKIGBWDJNTKX-UHFFFAOYSA-N 1-(dichloromethyl)-4-phenylbenzene Chemical group C1=CC(C(Cl)Cl)=CC=C1C1=CC=CC=C1 RAZKIGBWDJNTKX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- -1 polyoxymethylene Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/32—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by introduction of halogenated alkyl groups into ring compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
(57)【要約】
【課題】 本発明は、ビフェニルをクロロメチル化して
４，４’−ビスクロロメチルビフェニルを製造する方法
において、塩化チオニルを多量に使用することなく、
４，４’−ビスクロロメチルビフェニルを短時間でかつ
高收率で製造することができ、しかも反応温度の制御が
容易である方法を提供することを課題とする。
【解決手段】 本発明の課題は、ビフェニルを塩化亜鉛
の存在下にホルムアルデヒド重合物及び塩素化剤と反応
させて４，４’−ビスクロロメチルビフェニルを製造す
るに当たり、塩素化剤として塩化水素と塩化チオニルを
併用することを特徴とする４，４’−ビスクロロメチル
ビフェニルの製造方法によって達成される。PROBLEM TO BE SOLVED: To provide a method for producing 4,4'-bischloromethylbiphenyl by chloromethylating biphenyl without using a large amount of thionyl chloride.
It is an object of the present invention to provide a method capable of producing 4,4′-bischloromethylbiphenyl in a short time and at a high yield, and in which the reaction temperature is easily controlled. The object of the present invention is to produce 4,4′-bischloromethylbiphenyl by reacting biphenyl with a formaldehyde polymer and a chlorinating agent in the presence of zinc chloride. This is achieved by a method for producing 4,4′-bischloromethylbiphenyl, which comprises using thionyl chloride in combination.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、蛍光増白剤やエポ
キシ樹脂原料などの合成中間体として有用な化合物であ
る４，４’−ビスクロロメチルビフェニルの製造方法に
関する。The present invention relates to a method for producing 4,4'-bischloromethylbiphenyl which is a compound useful as a synthetic intermediate such as a fluorescent whitening agent or a raw material for an epoxy resin.
【０００２】[0002]
【従来の技術】ビフェニルをクロロメチル化して４，
４’−ビスクロロメチルビフェニルを製造する方法とし
ては、（１）ビフェニルをシクロヘキサン溶媒中で塩化
亜鉛の存在下にパラホルムアルデヒド及び塩化水素と反
応させる方法（特公昭４６−２９９０８号公報）、
（２）ビフェニルを不活性溶媒中で塩化亜鉛の存在下に
ホルムルデヒド重合物及び塩化チオニルと反応させる方
法（特開平３−１８８０２９号公報）が知られている。
しかしながら、（１）の方法では、反応時間が２４時間
と長いために生産性に問題がある。また、（２）の方法
では、反応時間は比較的短いものの、高価な塩化チオニ
ルを多量に使用する必要があることから、副生するイオ
ウ化合物の処理なども含め、経済性に問題があり、更に
発熱反応であることから、反応温度の制御が難しく收率
の低下を引き起こすという問題があった。BACKGROUND OF THE INVENTION Biphenyl is chloromethylated to give 4,
Examples of the method for producing 4'-bischloromethylbiphenyl include (1) a method in which biphenyl is reacted with paraformaldehyde and hydrogen chloride in a cyclohexane solvent in the presence of zinc chloride (JP-B-46-29908).
(2) A method is known in which biphenyl is reacted with a formaldehyde polymer and thionyl chloride in an inert solvent in the presence of zinc chloride (JP-A-3-188029).
However, the method (1) has a problem in productivity because the reaction time is as long as 24 hours. In the method (2), although the reaction time is relatively short, it is necessary to use a large amount of expensive thionyl chloride. Therefore, there is a problem in economical efficiency including treatment of a by-product sulfur compound. Furthermore, since the reaction is exothermic, there has been a problem that it is difficult to control the reaction temperature and the yield is reduced.
【０００３】[0003]
【発明が解決しようとする課題】前記のような技術背景
に鑑み、本発明は、ビフェニルをクロロメチル化して
４，４’−ビスクロロメチルビフェニルを製造する方法
において、塩化チオニルを多量に使用することなく、
４，４’−ビスクロロメチルビフェニルを短時間でかつ
高收率で製造することができ、しかも反応温度の制御が
容易である方法を提供することを課題とする。SUMMARY OF THE INVENTION In view of the above technical background, the present invention provides a method for producing 4,4'-bischloromethylbiphenyl by chloromethylating biphenyl, wherein a large amount of thionyl chloride is used. Without
It is an object of the present invention to provide a method capable of producing 4,4′-bischloromethylbiphenyl in a short time and at a high yield, and in which the reaction temperature is easily controlled.
【０００４】[0004]
【課題を解決するための手段】本発明者らは前記の課題
を解決するために鋭意検討した結果、意外にも、塩素化
剤として塩化水素と塩化チオニルを併用する（特に、最
初に塩化水素を使用し、その後に塩化チオニルを使用し
て反応を行う）ことによって、４，４’−ビスクロロメ
チルビフェニルを高收率で製造できると共に、前記の課
題を全て解決できることを見いだした。即ち、本発明の
課題は、ビフェニルを塩化亜鉛の存在下にホルムアルデ
ヒド重合物及び塩素化剤と反応させて４，４’−ビスク
ロロメチルビフェニルを製造するに当たり、塩素化剤と
して塩化水素と塩化チオニルを併用することを特徴とす
る４，４’−ビスクロロメチルビフェニルの製造方法に
よって達成される。The present inventors have conducted intensive studies to solve the above-mentioned problems. As a result, surprisingly, hydrogen chloride and thionyl chloride are used in combination as chlorinating agents (particularly, hydrogen chloride is first used). , Followed by a reaction using thionyl chloride), whereby 4,4′-bischloromethylbiphenyl can be produced at a high yield and all the above-mentioned problems can be solved. That is, an object of the present invention is to produce 4,4'-bischloromethylbiphenyl by reacting biphenyl with a formaldehyde polymer and a chlorinating agent in the presence of zinc chloride. This is achieved by a method for producing 4,4′-bischloromethylbiphenyl, which comprises using
【０００５】[0005]
【発明の実施の形態】本発明で使用されるホルムアルデ
ヒド重合物としては、パラホルムアルデヒド、ポリオキ
シメチレン、トリオキサン等が挙げられるが、工業的に
はパラホルムアルデヒド（特に純度７５重量％以上のパ
ラホルムアルデヒド）が好ましい。ホルムアルデヒド重
合物は、ビフェニルに対して２．０〜３．０倍モル、特
に２．１〜２．６倍モル使用されることが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION Examples of the formaldehyde polymer used in the present invention include paraformaldehyde, polyoxymethylene, and trioxane. Industrially, paraformaldehyde (particularly, paraformaldehyde having a purity of 75% by weight or more) is used. Is preferred. The formaldehyde polymer is preferably used in an amount of 2.0 to 3.0 times mol, particularly 2.1 to 2.6 times mol of biphenyl.
【０００６】塩化亜鉛は、ビフェニルに対して０．３〜
１．０倍モル、特に０．５〜０．８倍モル使用されるこ
とが好ましい。塩化亜鉛の純度は高いほうが好ましく、
特に純度９０重量５以上のものが好ましい。[0006] Zinc chloride is used in an amount of 0.3 to
It is preferably used in a 1.0-fold molar amount, particularly 0.5 to 0.8-fold molar amount. The higher the purity of zinc chloride, the better,
Particularly, those having a purity of 90% by weight or more are preferable.
【０００７】本発明では、塩素化剤として塩化水素と塩
化チオニルが併用される。特に、本発明では、塩素化剤
として最初に塩化水素（ガス）を使用し、その後に塩化
チオニルを使用して反応を行うことが好ましい。塩化水
素（ガス）は、ビフェニルに対して０．８〜４．０倍モ
ル、特に１．０〜３．０倍モル使用されることが好まし
い。塩化チオニルは、ビフェニルに対して０．３〜０．
８倍モル、特に０．４〜０．７倍モル使用されることが
好ましい。なお、塩化水素（ガス）は塩化チオニルに対
して０．８〜８．０倍モル、特に１．０〜６．０倍モル
使用されることが好ましい。In the present invention, hydrogen chloride and thionyl chloride are used in combination as a chlorinating agent. In particular, in the present invention, it is preferable to first use hydrogen chloride (gas) as a chlorinating agent, and then to carry out the reaction using thionyl chloride. Hydrogen chloride (gas) is preferably used in a molar amount of 0.8 to 4.0 times, particularly 1.0 to 3.0 times the molar amount of biphenyl. Thionyl chloride is used in an amount of 0.3 to 0.1 with respect to biphenyl.
It is preferably used in a molar amount of 8 times, especially 0.4 to 0.7 times. The hydrogen chloride (gas) is preferably used in a molar amount of 0.8 to 8.0 times, particularly 1.0 to 6.0 times the molar amount of thionyl chloride.
【０００８】反応溶媒は反応に不活性な溶媒であれば使
用可能であり、例えば、ｎ−ヘプタン、シクロヘキサ
ン、ジクロロエタン、クロロホルム等の脂肪族炭化水素
が好適に使用される。これら溶媒は、ビフェニルに対し
て０．８〜５．０重量倍、特に１．０〜３．０重量倍使
用されることが好ましい。[0008] The reaction solvent can be used as long as it is a solvent inert to the reaction. For example, aliphatic hydrocarbons such as n-heptane, cyclohexane, dichloroethane and chloroform are preferably used. These solvents are preferably used in an amount of 0.8 to 5.0 times by weight, particularly 1.0 to 3.0 times by weight, based on biphenyl.
【０００９】本発明の反応は、例えば、ビフェニル、パ
ラホルムアルデヒド、塩化亜鉛及び反応溶媒を入れた反
応器に所定量の塩化水素（ガス）を導入し、次いで所定
量の塩化チオニルを滴下する方法によって行われる。本
発明では、このように、最初に塩化水素（ガス）を供給
し、その後、更に塩化チオニルを供給して反応を行うこ
とが好ましい。なお、反応温度は３０〜７０℃、特に４
０〜６０℃であることが好ましい。反応圧は通常は常圧
であるが、使用される反応溶媒や反応温度によっては加
圧でも差し支えない。反応後、生成した４，４’−ビス
クロロメチルビフェニルは濾過、再結晶等により分離精
製される。The reaction of the present invention is carried out, for example, by introducing a predetermined amount of hydrogen chloride (gas) into a reactor containing biphenyl, paraformaldehyde, zinc chloride and a reaction solvent, and then dropwise adding a predetermined amount of thionyl chloride. Done. In the present invention, as described above, it is preferable to supply hydrogen chloride (gas) first and then supply thionyl chloride to carry out the reaction. The reaction temperature is 30 to 70 ° C., particularly 4 ° C.
The temperature is preferably 0 to 60 ° C. The reaction pressure is usually normal pressure, but may be increased depending on the reaction solvent used and the reaction temperature. After the reaction, the produced 4,4'-bischloromethylbiphenyl is separated and purified by filtration, recrystallization and the like.
【００１０】[0010]
【実施例】次に、実施例及び比較例を挙げて本発明を具
体的に説明する。なお、以下に示すＧＣ純度はガスクロ
マトグラフィー分析における純度（面積％）を示す。 実施例１ 冷却管、温度計、ガス導入管及び攪拌機を備えた内容積
３００ｍｌの４つ口フラスコに、ビフェニル（０．３０
モル）、９４重量％パラホルムアルデヒド（０．６６モ
ル）、９８重量％塩化亜鉛（０．１８モル）及びシクロ
ヘキサン６０ｇを入れ、５０℃で攪拌しながら、塩化水
素ガスを８０ｍｌ／ｍｉｎで３時間導入して反応を行っ
た。その後、塩化水素ガスの導入を止め、５０℃で攪拌
しながら、滴下ロートより塩化チオニル（０．１５モ
ル）を２時間で滴下して更に４時間反応を続けた。この
間、発熱は殆ど認められなかった。反応終了後、反応液
を室温まで冷却し、水５０ｍｌとシクロヘキサン６０ｍ
ｌを加えて１０分間攪拌して、吸引濾過により４，４’
−ビスクロロメチルビフェニルを分離した。この４，
４’−ビスクロロメチルビフェニルを更にメタノール１
２０ｍｌで洗浄して室温で２４時間減圧乾燥し、乾燥品
５３．１ｇを得た。乾燥品のＧＣ純度（９３．５％）よ
り求めた收率は６５．９％であった。そして、この乾燥
品をシクロヘキサンより再結晶して、融点：１３６〜１
３６℃、ＧＣ純度：９９．０％の無色結晶を得た。Next, the present invention will be described specifically with reference to examples and comparative examples. The GC purity shown below indicates the purity (area%) in gas chromatography analysis. Example 1 Biphenyl (0.30 mL) was placed in a 300 ml four-necked flask equipped with a cooling pipe, a thermometer, a gas introduction pipe, and a stirrer.
Mol), 94 wt% paraformaldehyde (0.66 mol), 98 wt% zinc chloride (0.18 mol) and 60 g of cyclohexane, and introduce hydrogen chloride gas at 80 ml / min for 3 hours while stirring at 50 ° C. The reaction was performed. Thereafter, the introduction of hydrogen chloride gas was stopped, and while stirring at 50 ° C., thionyl chloride (0.15 mol) was added dropwise from the dropping funnel over 2 hours, and the reaction was continued for another 4 hours. During this time, little heat was generated. After completion of the reaction, the reaction solution was cooled to room temperature, and 50 ml of water and 60 m of cyclohexane were used.
and stirred for 10 minutes.
-Bischloromethylbiphenyl was separated. This 4,
Add 4'-bischloromethylbiphenyl to methanol 1
After washing with 20 ml and drying under reduced pressure at room temperature for 24 hours, 53.1 g of a dried product was obtained. The yield determined from the GC purity (93.5%) of the dried product was 65.9%. The dried product is recrystallized from cyclohexane to give a melting point of 136 to 1
Colorless crystals having a temperature of 36 ° C. and a GC purity of 99.0% were obtained.
【００１１】実施例２ 反応温度を４０℃に変えて、塩化水素ガスを４時間導入
した後、塩化チオニル０．１７モルを２時間で滴下した
ほかは、実施例１と同様に反応を行って生成物を分離し
た。その結果、４，４’−ビスクロロメチルビフェニル
乾燥品５１．８ｇ（ＧＣ純度：９４．２％）が得られ、
その收率は６４．８％であった。Example 2 The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was changed to 40 ° C., hydrogen chloride gas was introduced for 4 hours, and then 0.17 mol of thionyl chloride was added dropwise over 2 hours. The product was separated. As a result, 51.8 g (GC purity: 94.2%) of 4,4′-bischloromethylbiphenyl dried product was obtained,
Its yield was 64.8%.
【００１２】比較例１ 塩化水素ガスを２４時間導入したのみで、塩化チオニル
を滴下しなかったほかは、実施例１と同様に反応を行っ
て生成物を分離した。但し、反応液が透明になった後
（塩化水素ガスの導入開始１時間後から）は反応温度を
３０℃にした。その結果、４，４’−ビスクロロメチル
ビフェニル乾燥品４８．８ｇ（ＧＣ純度：９４．０％）
が得られ、その收率は６０．９％であった。Comparative Example 1 A reaction was carried out in the same manner as in Example 1 except that only hydrogen chloride gas was introduced for 24 hours and thionyl chloride was not added dropwise, and a product was separated. However, after the reaction liquid became transparent (from 1 hour after the start of the introduction of hydrogen chloride gas), the reaction temperature was set to 30 ° C. As a result, 48.8 g of dried 4,4′-bischloromethylbiphenyl (GC purity: 94.0%)
Was obtained, and the yield was 60.9%.
【００１３】比較例２ 塩化水素ガスを９時間導入したほかは、比較例１と同様
に反応を行って生成物を分離した。その結果、４，４’
−ビスクロロメチルビフェニル乾燥品４０．４ｇ（ＧＣ
純度：８８．９％）が得られ、その收率は４７．７％で
あった。Comparative Example 2 A reaction was carried out in the same manner as in Comparative Example 1 except that hydrogen chloride gas was introduced for 9 hours to separate a product. As a result, 4,4 '
40.4 g of dried bischloromethylbiphenyl (GC
(Purity: 88.9%), and the yield was 47.7%.
【００１４】比較例３ 反応温度を４０℃に変えて、塩化水素ガスを導入するこ
となく、塩化チオニル０．３９モルを４時間で滴下した
ほかは、実施例１と同様に反応を行って生成物を分離し
た。なお、塩化チオニルの滴下中、発熱により２〜４℃
の温度上昇が認められ、反応温度は４２〜４４℃になっ
た。その結果、４，４’−ビスクロロメチルビフェニル
乾燥品４８．６ｇ（ＧＣ純度：９３．２％）が得られ、
その收率は６０．２％であった。Comparative Example 3 The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was changed to 40 ° C. and 0.39 mol of thionyl chloride was added dropwise over 4 hours without introducing hydrogen chloride gas. Things were separated. During the dropwise addition of thionyl chloride, heat was generated at 2 to 4 ° C.
Was observed, and the reaction temperature became 42 to 44 ° C. As a result, 48.6 g (GC purity: 93.2%) of 4,4′-bischloromethylbiphenyl dried product was obtained,
Its yield was 60.2%.
【００１５】比較例４ 反応温度を４５℃に変えたほかは、比較例２と同様に反
応を行って生成物を分離した。なお、塩化チオニルの滴
下中、発熱により２〜５℃の温度上昇が認められ、反応
温度は４７〜５０℃になった。その結果、４，４’−ビ
スクロロメチルビフェニル乾燥品３６．５ｇ（ＧＣ純
度：８４．８％）が得られ、その收率は４１．１％であ
った。実施例及び比較例の結果を表１に示す。Comparative Example 4 The reaction was carried out in the same manner as in Comparative Example 2 except that the reaction temperature was changed to 45 ° C., and the product was separated. During the dropwise addition of thionyl chloride, a temperature rise of 2 to 5 ° C. was observed due to heat generation, and the reaction temperature became 47 to 50 ° C. As a result, 36.5 g (GC purity: 84.8%) of a dried 4,4′-bischloromethylbiphenyl product was obtained, and the yield was 41.1%. Table 1 shows the results of Examples and Comparative Examples.
【００１６】[0016]
【表１】 [Table 1]
【００１７】[0017]
【発明の効果】本発明により、ビフェニルをクロロメチ
ル化して４，４’−ビスクロロメチルビフェニルを製造
する方法において、塩化チオニルを多量に使用すること
なく、４，４’−ビスクロロメチルビフェニルを短時間
でかつ高收率で製造することができる。また、この方法
によれば、反応温度の制御が容易であることから、反応
温度の上昇によって收率の低下を引き起こすこともな
く、また塩化チオニルの使用量を大幅に低減できるた
め、副生するイオウ化合物の処理なども容易になる。According to the present invention, in a method for producing 4,4'-bischloromethylbiphenyl by chloromethylating biphenyl, 4,4'-bischloromethylbiphenyl can be used without using a large amount of thionyl chloride. It can be manufactured in a short time and at a high yield. Further, according to this method, since the reaction temperature is easily controlled, a decrease in the yield is not caused by an increase in the reaction temperature, and the amount of thionyl chloride used can be significantly reduced. It also facilitates the treatment of sulfur compounds.
Claims (3)
アルデヒド重合物及び塩素化剤と反応させて４，４’−
ビスクロロメチルビフェニルを製造するに当たり、塩素
化剤として塩化水素と塩化チオニルを併用することを特
徴とする４，４’−ビスクロロメチルビフェニルの製造
方法。1. The reaction of biphenyl with a formaldehyde polymer and a chlorinating agent in the presence of zinc chloride to give 4,4'-
A process for producing 4,4'-bischloromethylbiphenyl, which comprises using hydrogen chloride and thionyl chloride as chlorinating agents in producing bischloromethylbiphenyl.
し、その後に塩化チオニルを使用して反応を行うことを
特徴とする請求項１記載の４，４’−ビスクロロメチル
ビフェニルの製造方法。2. The process for producing 4,4'-bischloromethylbiphenyl according to claim 1, wherein the reaction is carried out first using hydrogen chloride as a chlorinating agent and thereafter using thionyl chloride. .
〜８．０倍モル使用することを特徴とする請求項１記載
の４，４’−ビスクロロメチルビフェニルの製造方法。3. Hydrogen chloride is added in an amount of 0.8 to thionyl chloride.
The method for producing 4,4'-bischloromethylbiphenyl according to claim 1, wherein the molar amount is from 8.0 to 8.0 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29642196A JPH10139699A (en) | 1996-11-08 | 1996-11-08 | Method for producing 4,4'-bischloromethylbiphenyl |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29642196A JPH10139699A (en) | 1996-11-08 | 1996-11-08 | Method for producing 4,4'-bischloromethylbiphenyl |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10139699A true JPH10139699A (en) | 1998-05-26 |
Family
ID=17833333
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29642196A Pending JPH10139699A (en) | 1996-11-08 | 1996-11-08 | Method for producing 4,4'-bischloromethylbiphenyl |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10139699A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267870A (en) * | 2011-07-18 | 2011-12-07 | 扬州市中宝银鹏合成材料有限公司 | Production process of 4,4'-bis(chloromethyl)-biphenyl |
| CN107473927A (en) * | 2017-08-23 | 2017-12-15 | 湖北三才堂化工科技有限公司 | A kind of preparation technology of biphenyl-benzyl dichloride |
-
1996
- 1996-11-08 JP JP29642196A patent/JPH10139699A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267870A (en) * | 2011-07-18 | 2011-12-07 | 扬州市中宝银鹏合成材料有限公司 | Production process of 4,4'-bis(chloromethyl)-biphenyl |
| CN107473927A (en) * | 2017-08-23 | 2017-12-15 | 湖北三才堂化工科技有限公司 | A kind of preparation technology of biphenyl-benzyl dichloride |
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