JPH0523258B2 - - Google Patents
Info
- Publication number
- JPH0523258B2 JPH0523258B2 JP63129596A JP12959688A JPH0523258B2 JP H0523258 B2 JPH0523258 B2 JP H0523258B2 JP 63129596 A JP63129596 A JP 63129596A JP 12959688 A JP12959688 A JP 12959688A JP H0523258 B2 JPH0523258 B2 JP H0523258B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- halogenated
- reaction
- antimony
- sulfone
- 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
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical class C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 12
- 150000001555 benzenes Chemical class 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 150000003460 sulfonic acids Chemical class 0.000 claims description 7
- 150000001462 antimony Chemical class 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 8
- 229910052787 antimony Inorganic materials 0.000 description 8
- -1 aromatic sulfone compound Chemical class 0.000 description 8
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 4
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- IBRQUKZZBXZOBA-UHFFFAOYSA-N 1-chloro-3-(3-chlorophenyl)sulfonylbenzene Chemical compound ClC1=CC=CC(S(=O)(=O)C=2C=C(Cl)C=CC=2)=C1 IBRQUKZZBXZOBA-UHFFFAOYSA-N 0.000 description 3
- ZLYBFBAHAQEEQQ-UHFFFAOYSA-N 4-chlorobenzenesulfonyl chloride Chemical compound ClC1=CC=C(S(Cl)(=O)=O)C=C1 ZLYBFBAHAQEEQQ-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- PLVUIVUKKJTSDM-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)sulfonylbenzene Chemical compound C1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(F)C=C1 PLVUIVUKKJTSDM-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910018287 SbF 5 Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- MNURPFVONZPVLA-UHFFFAOYSA-N 2-chlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1Cl MNURPFVONZPVLA-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 125000006414 CCl Chemical group ClC* 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- WIRUZQNBHNAMAB-UHFFFAOYSA-N benzene;cyclohexane Chemical compound C1CCCCC1.C1=CC=CC=C1 WIRUZQNBHNAMAB-UHFFFAOYSA-N 0.000 description 1
- IDIPWEYIBKUDNY-UHFFFAOYSA-N benzenesulfonyl fluoride Chemical class FS(=O)(=O)C1=CC=CC=C1 IDIPWEYIBKUDNY-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- PBWZKZYHONABLN-UHFFFAOYSA-N difluoroacetic acid Chemical compound OC(=O)C(F)F PBWZKZYHONABLN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 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)
Description
【発明の詳細な説明】
〔技術分野の説明及び産業上の利用分野〕
本発明は、４，4′−ジハロゲン化ジフエニルス
ルホンの製造方法に関し、さらに詳しくは、ハロ
ゲン化アンチモンの共存下、ハロゲン化スルホン
酸とハロゲン化ベンゼンから温和な条件で効率よ
く、４，4′−ジハロゲン化ジフエニルスルホンを
製造する方法に関するものである。Detailed Description of the Invention [Description of Technical Field and Field of Industrial Application] The present invention relates to a method for producing 4,4'-dihalogenated diphenyl sulfone, and more specifically, the present invention relates to a method for producing 4,4'-dihalogenated diphenyl sulfone. The present invention relates to a method for efficiently producing 4,4'-dihalogenated diphenyl sulfone from halogenated sulfonic acid and halogenated benzene under mild conditions.
４，4′−ジハロゲン化ジフエニルスルホンは、
一般に透明で耐熱性に優れたポリスルホン，ポリ
エーテルスルホン，あるいはエポキシ硬化剤，医
薬，農薬等の原料として有用な物質である。 4,4′-dihalogenated diphenyl sulfone is
Generally, it is transparent and has excellent heat resistance, such as polysulfone or polyethersulfone, or it is a useful material as a raw material for epoxy curing agents, medicines, agricultural chemicals, etc.
〔従来の技術及び産業上の利用分野〕
４，4′−ジクロロジフエニルスルホンの製造法
に関しては、多くの研究例があり、大別すると次
のようになる。[Prior Art and Industrial Application Fields] There are many research examples regarding the production method of 4,4'-dichlorodiphenyl sulfone, which can be roughly classified as follows.
(1) クロロベンゼンと三酸化硫黄を反応させてク
ロロベンゼンスルホン酸を得、ついで塩化チオ
ニルと反応させて４−クロロベンゼンスルホニ
ルクロライドに転化させ、しかる後塩化第二鉄
の存在下にクロロベンゼンと反応させて、４，
4′−ジクロロジフエニルスルホンを合成する方
法（特公昭59−29586，特公昭56−5386）
(2) クロロベンゼンとクロロスルホン酸を反応さ
せて、４−クロロベンゼンスルホニルクロライ
ドを得、ついで塩化第二鉄の存在下にクロロベ
ンゼンと反応させて、４，4′−ジクロロジフエ
ニルスルホンを合成する方法（特開昭58−
74655，特開昭58−206553）
(3) クロロベンゼンと硫酸を加圧下に加熱して、
４，4′−ジクロロジフエニルスルホンを合成す
る方法（特開昭49−76834）
しかしながら、上記いずれの方法も尚改善され
るべき種々の問題点を有しており、工業的方法と
しては決して満足できるものではない。即ち、上
記(1)の方法は３段階の反応であり、各ステツプ毎
に反応条件及び添加方法を変更しなければならず
繁雑である。また、(2)の方法は２段階の反応であ
り、一旦、４−クロロフエニルスルホニルクロラ
イドを単離するわずらわしさがある。(3)の方法は
１段反応であるが、加圧下、長時間の加熱を要
し、異性体の分離という繁雑さがある。(1) Reacting chlorobenzene with sulfur trioxide to obtain chlorobenzenesulfonic acid, then reacting with thionyl chloride to convert it to 4-chlorobenzenesulfonyl chloride, and then reacting with chlorobenzene in the presence of ferric chloride, 4,
Method for synthesizing 4'-dichlorodiphenylsulfone (Japanese Patent Publication No. 59-29586, Japanese Patent Publication No. 56-5386) (2) Reacting chlorobenzene with chlorosulfonic acid to obtain 4-chlorobenzenesulfonyl chloride, followed by ferric chloride. A method for synthesizing 4,4'-dichlorodiphenyl sulfone by reacting it with chlorobenzene in the presence of
74655, JP 58-206553) (3) By heating chlorobenzene and sulfuric acid under pressure,
Method for synthesizing 4,4'-dichlorodiphenyl sulfone (Japanese Unexamined Patent Publication No. 49-76834) However, all of the above methods have various problems that still need to be improved, and are by no means satisfactory as industrial methods. It's not possible. That is, the method (1) above is a three-step reaction, and the reaction conditions and addition method must be changed for each step, which is complicated. Furthermore, method (2) is a two-step reaction, and it is troublesome to first isolate 4-chlorophenylsulfonyl chloride. Method (3) is a one-stage reaction, but it requires heating under pressure for a long time and is complicated by the separation of isomers.
本発明の目的とするところは、前述の既存合成
法のような欠点のない、工業的に容易な方法で
４，4′−ジハロゲン化フエニルスルホンの製造法
を提供することにある。 An object of the present invention is to provide a method for producing 4,4'-dihalogenated phenyl sulfone by an industrially easy method that does not have the drawbacks of the existing synthetic methods described above.
本発明者らは、超強酸中における芳香族化合物
のスルホン化反応に関して種々研究した結果、ハ
ロゲン化アンチモンの存在下、ハロゲン化ベンゼ
ンとハロゲン化スルホン酸の反応により常温，常
圧の温和な条件下、１段反応で４，4′−ジハロゲ
ン化ジフエニルスルホンを高収率に合成しうるこ
とを見出し、本発明を完成するに至つた。
As a result of various studies on the sulfonation reaction of aromatic compounds in super strong acids, the present inventors found that the reaction between halogenated benzene and halogenated sulfonic acid in the presence of halogenated antimony was performed under mild conditions at room temperature and pressure. The inventors have discovered that 4,4'-dihalogenated diphenyl sulfone can be synthesized in high yield in a one-stage reaction, and have completed the present invention.
すなわち本発明は、ハロゲン化ベンゼンから常
温常圧で芳香族スルホン化合物を合成するに際
し、硫黄化合物として酸強度の高いフルオロスル
ホン酸又はクロロスルホン酸を用い、触媒として
５−フツ化アンチモン又は、５−塩化アンチモン
等を用いることにある。ハロゲン化スルホン酸と
ハロゲン化アンチモンを混合して得られる超強酸
の酸強度は、100％硫酸の100倍以上であり、その
ために、従来の硫酸やクロロスルホン酸中では不
可能であつた反応が可能になるものである。なぜ
ならば超強酸系では次式に示すスルホカチオン
〔SO2X+〕が安定に存在し、芳香族化合物への求
電子攻撃を行うので、芳香族化合物への求電子置
換反応が起こりやすくなる。代表的な反応式を次
に示す。 That is, in the present invention, when synthesizing an aromatic sulfone compound from halogenated benzene at room temperature and normal pressure, fluorosulfonic acid or chlorosulfonic acid with high acid strength is used as a sulfur compound, and 5-antimony fluoride or 5-antimony fluoride is used as a catalyst. The purpose is to use antimony chloride, etc. The acid strength of the super strong acid obtained by mixing halogenated sulfonic acid and halogenated antimony is more than 100 times that of 100% sulfuric acid, and therefore reactions that are impossible in conventional sulfuric acid or chlorosulfonic acid are possible. It becomes possible. This is because in a super-strong acid system, the sulfo cation [SO 2 A typical reaction formula is shown below.
FSO3Ｈ＋SbF5→〔FSO2 +〕＋〔OH-〕SbF5
反応は上式のように、４−ハロゲン化フエニル
スルホニルフルオライド（またはクロライド）が
一旦生成し、しかる後ハロゲン化アンチモンの存
在下フリーデルクラフト型反応により、４，4′−
ジハロゲン化ジフエニルスルホンが生成すると考
えられる。FSO 3 H + SbF 5 → [FSO 2 + ] + [OH - ] SbF 5 As shown in the above formula, the reaction first generates 4-halogenated phenylsulfonyl fluoride (or chloride), and then undergoes a Friedel-Crafts type reaction in the presence of antimony halide to form 4,4'-
It is thought that dihalogenated diphenyl sulfone is produced.
超強酸中にハロゲン化ベンゼンを加え、室温で
攪拌するだけで、スルホン化が容易におこり、一
つの反応容器で４，４−ジハロゲン化ジフエニル
スルホンを得ることが可能になつた。 By simply adding halogenated benzene to a super strong acid and stirring at room temperature, sulfonation can easily occur, making it possible to obtain 4,4-dihalogenated diphenylsulfone in one reaction vessel.
ハロゲン化スルホン酸としては、フルオロスル
ホン酸，クロロスルホン酸等が用いられる。 As the halogenated sulfonic acid, fluorosulfonic acid, chlorosulfonic acid, etc. are used.
ハロゲン化アンチモンとしては、５−フツ化ア
ンチモン、５−塩化アンチモンなどが挙げられ
る。これらのハロゲン化アンチモンは、５−フツ
化タリウム、５−フツ化ヒ素、５−フツ化ニオ
ブ、三フツ化ホウ素、三酸化イオウ、塩化アルミ
ニウム、三塩化鉄などのルイス酸と併用してもよ
い。 Examples of antimony halides include 5-antimony fluoride and 5-antimony chloride. These antimony halides may be used in combination with Lewis acids such as 5-thallium fluoride, 5-arsenic fluoride, 5-niobium fluoride, boron trifluoride, sulfur trioxide, aluminum chloride, and iron trichloride. .
溶媒としては、トリフルオロ酢酸，ジフルオロ
酢酸，トリクロロ酢酸，ジクロロ酢酸，モノクロ
ロ酢酸，硫酸等が用いられる。 As the solvent, trifluoroacetic acid, difluoroacetic acid, trichloroacetic acid, dichloroacetic acid, monochloroacetic acid, sulfuric acid, etc. are used.
原料のハロゲン化ベンゼン、またはハロゲン化
スルホン酸を過剰に用い、溶媒としての役割を果
たさせることも可能である。一般的な反応法とし
ては、ハロゲン化スルホン酸とハロゲン化アンチ
モンと溶媒の混合物中に室温でハロゲン化ベンゼ
ンを徐々に滴下し、数時間攪拌する。反応終了後
混合物を氷水に移し、析出した白色結晶をろ過に
より分離する。メタノール洗浄またはベンゼン−
シクロヘキサンからの再結晶により、４，4′−ジ
ハロゲン化ジフエニルスルホンの白色結晶が得ら
れる。 It is also possible to use an excess of the raw material halogenated benzene or halogenated sulfonic acid to serve as a solvent. As a general reaction method, halogenated benzene is gradually dropped into a mixture of halogenated sulfonic acid, halogenated antimony, and a solvent at room temperature, and the mixture is stirred for several hours. After the reaction is completed, the mixture is transferred to ice water, and the precipitated white crystals are separated by filtration. Methanol cleaning or benzene
Recrystallization from cyclohexane gives white crystals of 4,4'-dihalogenated diphenylsulfone.
NMR，赤外分光，質量分析，液クロ等により
分析した結果、４，4′−ジハロゲン化ジフエニル
スルホンが生成していることが確認された。 As a result of analysis by NMR, infrared spectroscopy, mass spectrometry, liquid chromatography, etc., it was confirmed that 4,4'-dihalogenated diphenyl sulfone was produced.
反応温度は室温付近が望ましく、60℃以上に加
熱すると、スルホン化合物の収率は低下する。反
応時間は６〜24時間の範囲で行われる。 The reaction temperature is preferably around room temperature; heating above 60°C will reduce the yield of the sulfone compound. The reaction time ranges from 6 to 24 hours.
本発明による４，4′−ジハロゲン化ジフエニル
スルホンの製造法においては、常温常圧、かつ一
段反応で高収率に異性体を副生することなく、容
易に目的とする４，4′−ジクロロジフエニルスル
ホンのみを製造することが可能になつた。従来法
に比べて、容易かつ高収率にスルホン化合物を合
成することが出来、製造プロセスが単純になり、
本発明は極めて工業的に有利な方法である。
In the method for producing 4,4'-dihalogenated diphenylsulfone according to the present invention, the desired 4,4'- It became possible to produce only dichlorodiphenyl sulfone. Compared to conventional methods, sulfone compounds can be synthesized easily and in high yield, and the manufacturing process is simplified.
The present invention is an extremely industrially advantageous method.
実施例
次に実施例により本発明をさらに詳細に説明す
る。Examples Next, the present invention will be explained in more detail with reference to Examples.
実施例 １
フルオロスルホン酸12ml（0.2モル），５−フツ
化アンチモン7.3ml（0.1モル），トリフルオロ酢
酸20mlを三ツ口フラスコに入れ、外部を冷却しな
がら、クロロベンゼン10.2ml（0.1モル）を徐々
に滴下する。室温で混合物をマグネテイツクスタ
ーラーにて攪拌する。Example 1 12 ml (0.2 mol) of fluorosulfonic acid, 7.3 ml (0.1 mol) of antimony 5-fluoride, and 20 ml of trifluoroacetic acid were placed in a three-necked flask, and while cooling the outside, 10.2 ml (0.1 mol) of chlorobenzene was gradually added. Drip. Stir the mixture with a magnetic stirrer at room temperature.
12時間後、反応混合物を氷水に移す。析出した
白色結晶をろ過により分離し、メタノール洗浄す
ると、融点145〜147℃の白色結晶12.20gが得られ
た。この化合物のIRを測定すると、1330，1160
cm-1に−SO2−の吸収、1585，1474cm-1にベンゼ
ン核の吸収、770，633cm-1にＣ−Clの吸収が測定
された。1HNMRケミカルシフトでは、δ7.7〜8.4
にベンゼン核のシグナルがみられた。液クロ分析
においてもODS−120Tのカラムを用いると、ジ
クロロジフエニルスルホンが確認され、得られた
化合物は、４，4′−ジクロロジフエニルスルホン
であることが確認された。４，4′−ジクロロジフ
エニルスルホンはクロロベンゼンを基準にして85
％の収率で生成していた。なお、溶媒のトリフル
オロ酢酸を用いない場合、４，4′−ジクロロジフ
エニルスルホンの収率は60％であつた。 After 12 hours, transfer the reaction mixture to ice water. The precipitated white crystals were separated by filtration and washed with methanol to obtain 12.20 g of white crystals with a melting point of 145-147°C. When measuring the IR of this compound, it is 1330, 1160
Absorption of -SO2- was measured at cm -1 , absorption of benzene nuclei at 1585 and 1474 cm -1 , and absorption of C-Cl at 770 and 633 cm -1 . 1HNMR chemical shift is δ7.7~8.4
A benzene nuclear signal was seen in the sample. When an ODS-120T column was used in liquid chromatography analysis, dichlorodiphenyl sulfone was confirmed, and the obtained compound was confirmed to be 4,4'-dichlorodiphenyl sulfone. 4,4'-dichlorodiphenyl sulfone is 85% based on chlorobenzene.
% yield. Note that when the solvent trifluoroacetic acid was not used, the yield of 4,4'-dichlorodiphenyl sulfone was 60%.
実施例 ２
フルオロスルホン酸12ml，５−塩化アンチモン
12.6mlの混合物中に、クロロベンゼン10.2mlを
徐々に滴下する。室温にて８時間、マグネテイツ
クスターラーにより攪拌する。Example 2 Fluorosulfonic acid 12ml, 5-antimony chloride
Gradually drop 10.2 ml of chlorobenzene into the 12.6 ml mixture. Stir with a magnetic stirrer at room temperature for 8 hours.
反応混合物を氷水に移し、生成物をろ過により
分離する。液クロ，IR，NMR等により分析した
結果、融点145〜147℃の白色結晶である４，4′−
ジクロロジフエニルスルホン5.8gが、クロロベン
ゼンを基準にして40％の収率で得られた。 The reaction mixture is transferred to ice water and the product is separated by filtration. As a result of analysis by liquid chromatography, IR, NMR, etc., it was found that 4,4'-
5.8 g of dichlorodiphenyl sulfone were obtained with a yield of 40% based on chlorobenzene.
実施例 ３
フルオロスルホン酸12ml，５−フツ化アンチモ
ン7.3ml，トリフルオロ酢酸20mlを三ツ口フラス
コに入れ、30℃でフロロベンゼン9.6mlを徐々に
滴下し、攪拌する。８時間後、反応混合物を氷水
に移す。析出した生成物をベンゼン−シクロヘキ
サンにて再結晶すると、融点98〜99℃の白色結晶
10.2gが得られた。この化合物のIRを測定すると、
1325，1155cm-1に−SO2−の吸収、1490，1585cm
−１にベンゼン核の吸収があり、1HNMRケミカル
シフトでは、7.0〜8.0ppmにベンゼン核のシグナ
ルが測定され、この化合物は４，4′−ジフロロジ
フエニルスルホンであることが確認された。４，
4′−ジフロロジフエニルスルホンは、フロロベン
ゼンを基準にして80％の収率で生成していた。Example 3 12 ml of fluorosulfonic acid, 7.3 ml of antimony 5-fluoride, and 20 ml of trifluoroacetic acid are placed in a three-necked flask, and 9.6 ml of fluorobenzene is gradually added dropwise at 30°C, followed by stirring. After 8 hours, transfer the reaction mixture to ice water. When the precipitated product is recrystallized from benzene-cyclohexane, white crystals with a melting point of 98-99℃ are obtained.
10.2g was obtained. When we measure the IR of this compound, we get
Absorption of −SO 2 − at 1325, 1155 cm −1 , 1490, 1585 cm
There was absorption of a benzene nucleus at -1 , and in 1 HNMR chemical shift, a signal of a benzene nucleus was measured at 7.0 to 8.0 ppm, and this compound was confirmed to be 4,4'-difluorodiphenylsulfone. 4,
4'-difluorodiphenylsulfone was produced in a yield of 80% based on fluorobenzene.
Claims (1)
ベンゼンとハロゲン化スルホン酸とを反応させる
ことを特徴とする４，4′−ジハロゲン化ジフエニ
ルスルホンの製造方法。1. A method for producing 4,4'-dihalogenated diphenyl sulfone, which comprises reacting halogenated benzene and halogenated sulfonic acid in the presence of halogenated antimony.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63129596A JPH01299266A (en) | 1988-05-26 | 1988-05-26 | Production of 4,4'-dihalogenated diphenyl sulfone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63129596A JPH01299266A (en) | 1988-05-26 | 1988-05-26 | Production of 4,4'-dihalogenated diphenyl sulfone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01299266A JPH01299266A (en) | 1989-12-04 |
| JPH0523258B2 true JPH0523258B2 (en) | 1993-04-02 |
Family
ID=15013359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63129596A Granted JPH01299266A (en) | 1988-05-26 | 1988-05-26 | Production of 4,4'-dihalogenated diphenyl sulfone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01299266A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60197655A (en) * | 1983-12-22 | 1985-10-07 | ロ−ヌ−プ−ラン・スペシアリテ・シミ−ク | Sulfonylation |
-
1988
- 1988-05-26 JP JP63129596A patent/JPH01299266A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60197655A (en) * | 1983-12-22 | 1985-10-07 | ロ−ヌ−プ−ラン・スペシアリテ・シミ−ク | Sulfonylation |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01299266A (en) | 1989-12-04 |
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