WO1998058907A1 - Procede de fabrication de 4,4'-dihalogenodiphenylsulfone - Google Patents

Procede de fabrication de 4,4'-dihalogenodiphenylsulfone Download PDF

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Publication number
WO1998058907A1
WO1998058907A1 PCT/EP1998/003507 EP9803507W WO9858907A1 WO 1998058907 A1 WO1998058907 A1 WO 1998058907A1 EP 9803507 W EP9803507 W EP 9803507W WO 9858907 A1 WO9858907 A1 WO 9858907A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
oxides
group
reaction
chlorobenzene
Prior art date
Application number
PCT/EP1998/003507
Other languages
German (de)
English (en)
Inventor
Stefan Beckmann
Helmut Reichelt
Karl Beck
Klaus Friedrich
Eugen Gehrer
Thomas Plesnivy
Walter Opper
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DE1997126806 external-priority patent/DE19726806A1/de
Priority claimed from DE1997126805 external-priority patent/DE19726805A1/de
Priority claimed from DE1997126807 external-priority patent/DE19726807A1/de
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to CA002283894A priority Critical patent/CA2283894A1/fr
Priority to AU84379/98A priority patent/AU8437998A/en
Priority to EP98934947A priority patent/EP0993443A1/fr
Publication of WO1998058907A1 publication Critical patent/WO1998058907A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/14—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides

Definitions

  • the invention relates to a process for the preparation of 4,4'-dihalodiphenyl sulfone by reacting halogenobenzene with p-halogenosulfonyl chloride in the presence of
  • a homogeneous Friedel-Crafts catalyst for example AICI 3 or FeCl 3
  • AICI 3 or FeCl 3 was used in at least a molar amount, which cannot be recovered during processing, but must be decomposed. This leads to problems of disposal of the hydrolyzed aluminum or iron chloride, which are toxic or corrosive waste.
  • heterogeneous catalysts based on acidic "clays”, which term also includes the oxides of aluminum, silicon, zirconium or titanium, can be used for alkylations.
  • these catalysts only contain the “clays” as supports on which aluminum chloride has been applied, and their use for sulfonylations is neither described nor suggested.
  • This object was achieved according to the invention with a process for the preparation of 4, 4'-dihalodiphenylsulfone, in which the halogen radicals can be the same or different, by reacting halobenzene with 4 -halophenylsulfonyl chloride in the liquid phase in the presence of a solid, acidic-centered catalyst with increased Temperature, characterized in that the reaction of 4 -halophenylsulfonyl chloride of the formula I.
  • X denotes chlorine, bromine or fluorine, with chlorine, bromine or fluorobenzene in the presence of a catalyst which is selected from one of the groups
  • Ki catalysts which consist of layer silicates which are essentially not doped with Lewis acids and which have negative layer charges saturated by protons, or which contain these as an essential constituent
  • K 2 ) catalysts which consist of zeolites in the acidic H form or contain these as an essential constituent
  • K 3 ) catalysts which consist of mixed oxides containing acid centers or contain these as essential constituents, the mixed oxides consisting of a combination of (a) oxides of titanium, zirconium, hafnium, tin, iron or Cr (III) on the one hand with (b) Oxides of vanadium, chromium (VI), molybdenum, tungsten or scandium on the other hand exist, or the mixed oxides are sulfated or phosphated oxides of group (a) and the mixed oxides have been calcined after their combination at temperatures of 450 to 800 ° C.
  • Substantially not doped with Lewis acids (group Ki) means that no, or practically no, Lewis acids have been applied to the layered silicates for the purpose of generating a catalytic activity caused by them. Rather, the acidic centers of the layered silicates are said to be essentially Bronsted centers which have been produced by exchanging the metal ions for protons in the layered silicates having negative excess charges.
  • layered silicates essentially not doped with Lewis acids are understood to mean those silicates which contain less than 1% by weight, based on the layered silicate, of Lewis acids and in particular those which are derived from Lewis acid applied separately - transition metals are completely free.
  • the sheet silicates of group Ki) to be used according to the invention are above all aluminum silicates; they belong to the clay minerals and are made up of Si0 2 ethedron and A1 2 0 3 octahedron layers, where part of the silicon in the tetrahedron layer is formed by trivalent cations, preferably aluminum and / or part of the aluminum in the octahedron layer by divalent ones Cations, preferably magnesium is replaced, so that negative stratified charges arise.
  • Layered silicates with negative charges occur naturally in the form of montmorillonites, vermiculites or hectorites or can also be synthesized.
  • montmorillonite which is converted into the H form by acid treatment.
  • examples are montmorillonite
  • the exchangeable cations contained in the natural or synthetic layer silicates are exchanged for protons. This is done in a manner known per se, e.g. by treatment 0 with sulfuric acid or hydrochloric acid.
  • pillared clays Since the protons are less temperature stable than layer silicates containing alkali or alkaline earth ions, so-called "pillared clays" can also be used, in which layers 5 are supported against one another.
  • the production of such "pillared clays” is in Figuras, Catal. Rev. Be. Closely. 30 (1988) 457 and Jones, Catal. Today (2 (1988) 357. The information given there is hereby incorporated by reference and is intended to be incorporated here.
  • layered silicates with negative layer charges which are saturated by protons, are: montmorillonite, vermiculite and hectorite.
  • the zeolites used for use as a group K) catalyst are, for example, those of the acid H form of the structure types MFI, MEL, BOG, BEA, EMT; MOR, FAU, MTW, LTL, NES, CON or MCM-22 according to the structure classification from WM Meier, DH Olson, Ch. Baerlocher, Atlas of Zeolithe Structure Types, Elsevier, 4 th ed.,
  • the acidic H form of 12-ring zeolites of the structure type BETA, Y, EMT and mordenite, and 10-ring zeolites of the Pentasil type are preferred.
  • the zeolites can also contain boron, gallium, iron or titanium in the framework. They can also be partially exchanged with elements of the IB, IIB, IIIB, IIIA or VIIIB group, as well as with the elements of the lanthanides.
  • Mixed oxides of group K 3 ) to be used according to the invention are, in particular, so-called superacid mixed oxides which have been described several times in the literature.
  • RJ Gillesie Acc. Chem. Res. 1, (1968) 202 and RJ Gillespie and TE Peel, Adv. Phys. Org. Chem. 9 (972) 1.
  • Suitable sulfated or phosphated metal oxides of group (a) are, in particular, phosphated or sulfated zirconium oxide or titanium oxide, which may also contain further elements, such as iron, cobalt or manganese.
  • Zr0S0 4 (S content 0.5 to 4 mol%) Zr0 2 P 2 O 5 (P 2 0 5 content 3 to 20 mol%) Fe 2 0 3 P 2 0 5 (P 2 0 5 content 3 to 20 mol%) Co / Mn / Zr0 2 S0 4 (S content 0.5 to 4 mol%);
  • Preferred superacid mixed metal oxides of groups (a) and (b) are those which contain zirconium, titanium, iron, tin or Cr (III) on the one hand and tungsten or molybdenum on the other hand.
  • the molar ratio of the oxides group (a) to group (b) is usually 70 to 30 to 90 to 10.
  • the reaction according to the invention generally takes place at temperatures of 80 to 300 ° C., preferably 110 to 220 ° C. and in particular 130 to 200 ° C.
  • the reaction is usually carried out at normal pressure or in a closed vessel at the autogenous pressure of the reaction mixture, but elevated pressure up to 50, preferably up to 30, bar is also possible.
  • 4, 4'-dichlorophenyl sulfone is prepared by reacting 4-chlorophenyl sulfonyl chloride with chlorobenzene.
  • the starting material chlorobenzene is used in excess, e.g. in a 1 to 100, preferably 5 to 20 and in particular a 5 to 15 molar excess over the amount of chlorophenylsulfonyl chloride.
  • the chlorobenzene serves as a solvent.
  • another solvent e.g. a hydrocarbon, preferably such a hydrocarbon may be added that e.g. the desired reaction temperature is achieved at normal pressure.
  • the catalytic reaction is generally carried out in the liquid phase in the suspension mode or preferably over a fixed catalyst, in a continuously flowed reactor, the hydrochloric acid liberated being drained off and the reaction mixture containing the product being drawn off for working up by distillation. After fractionation into product, unreacted chlorobenzene and optionally solvent, the latter are returned to the reaction.
  • The, 4 '-dichlorodiphenyl sulfone is used in a manner known per se e.g. purified by solvent crystallization from toluene, chlorobenzene or methanol. It is obtained in very good purity in yields of 50 to 95% of theory. Th. Based on p-chlorophenylsulfonyl chloride used.
  • the reaction according to the invention is carried out continuously as shown in FIG. 1 in such a way that the catalyst is fixed in reactor A and from below the reaction mixture from the starting materials chlorobenzene (1) and 4-chlorophenylsulfonyl chloride (2) and recycled chlorobenzene (4th ) is flowed through without pressure.
  • the reaction temperature is, for example, 80 to 300 ° C. and the excess of chlorobenzene is 10 molar.
  • the reaction mixture, from which the hydrogen chloride released escapes via line (5), is transferred via line (3) to a distillation column (B) and separated into the product (6) and chlorobenzene (4) to be recycled, which is still to be purified .
  • the heterogeneous catalyst remains active over a longer period of time. It can then be reactivated, for example by burning in air at temperatures above 450 ° C. This makes the new process particularly advantageous over conventional synthesis for economic and environmental reasons.
  • Example 4 A tube reactor filled with the catalyst according to Example 1 was flowed through from bottom to top with a mixture of 4-chlorobenzenesulfonyl chloride and chlorobenzene in a ratio of 1:10. The released HCl gas was discharged at the top of the tubular reactor and passed through an exhaust gas scrubber. The raw reactor output was collected and the excess chlorobenzene was removed by distillation. When the 4-chlorobenzenesulfonyl chloride had completely converted, the yield was: 92% of theory. Th .. Use of catalysts from group K 2 ) Example 4
  • the beta zeolite was obtained as follows:
  • the Zr beta zeolite was obtained as follows:
  • beta zeolite 50 g were heated in a rotary tube furnace at 380 ° C. under nitrogen for 2 hours. The mixture was then cooled to room temperature and 8.9 g of ZrCl were added as a powder. The mixture was heated to 460 ° C. over the course of 25 minutes and this for 2 hours Temperature maintained (N 2 - current 10 1 / h). The product was then calcined at 550 ° C. for 3 hours.
  • a tube reactor filled with beta zeolite as a catalyst was flowed through from bottom to top with a mixture of 4-chlorobenzenesulfonyl chloride and chlorobenzene in a ratio of 1:10.
  • the HCl gas released was discharged at the top of the tubular reactor.
  • the reactor crude discharge was collected and the excess chlorobenzene was removed by distillation. With complete conversion of the 4-chlorobenzenesulfonyl chloride, the yield was: 91% of theory. Th ..
  • H-ZSM-5 100 g of H-ZSM-5 were suspended in 200 ml of water. A solution of 70 g of FeCl 2 - 4 H 2 0 in 200 ml of water was then added and the mixture was stirred at room temperature for 24 hours. The product was filtered off, washed free of chlorine, dried at 110 ° C. and calcined at 550 ° C. for 3 hours.
  • a solution of 53 g of tungstic acid and 112 g of 25% NH 3 solution was added to 200 g of TiO 2 powder. This mixture was kneaded for 150 minutes and then dried at 120 ° C. for 12 hours. The product was then sieved and calcined at 675 ° C for 2 hours.
  • a tube reactor (5 cm in diameter and 50 cm in length) filled with Zr0 2 S0 4 catalyst (produced according to Example 9) was continuously flowed through from bottom to top with a mixture of 4-chlorobenzenesulfonyl chloride and chlorobenzene in a ratio of 1:10.
  • the released HCl gas was discharged at the top of the tubular reactor and passed through an exhaust gas scrubber.
  • the raw reactor discharge was collected and the excess chlorobenzene was removed by distillation. With complete conversion of the chlorobenzenesulfonyl chloride, the yield was 91% of theory.
  • the catalysts according to Examples 12 to 15 were produced as follows:
  • Amorphous Zr (OH) hydrate (preparation analogous to Example 9) was impregnated with a solution of CO (N0 3 ) 2 , Mn (N0 3 ) and (NH) 2 S0. The product was evaporated in a rotary evaporator and then calcined at 625 ° C. for 2 hours.
  • Amorphous Zr (OH) 4 hydrate (preparation analogous to Example 9) was impregnated with a solution of (NH 4 ) 2 Mo0 4 in water. After evaporation, the product was calcined at 600 ° C. for 2 hours. The Mo0 3 content was 5%.
  • the catalysts of group K 3 to be used according to the invention give significantly better yields.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Procédé de fabrication de 4,4'-dihalogénodiphénylsulfone consistant à faire réagir un benzol halogéné avec un chlorure de 4-halogénophénylsulfonyle en phase liquide, en présence d'un catalyseur solide présentant des centres acides, à température élevée, caractérisé en ce qu'on fait réagir le chlorure de 4-halogénophénylsurlfonyle de formule (I), dans laquelle X désigne le chlore, le brome ou le fluor, avec un chlorobenzol, un bromobenzol ou un fluorobenzol, en présence d'un catalyseur choisi dans l'un des groupes ci-après: K1) catalyseurs renfermant essentiellement des silicates stratifiés, non dotés d'acides de Lewis, présentant des charges en couche négatives saturées par des protons, ou renfermant ceux-ci comme constituants essentiels, K2) catalyseurs renfermant des zéolites sous la forme H acide, ou renfermant ceux-ci comme constituants essentiels, ou K3) catalyseurs renfermant des oxydes mixtes présentant des centres acides ou renfermant ceux-ci comme constituants essentiels, lesdits oxydes mixtes comprenant une combinaison (a) d'oxydes de titane, zirconium, hafnium, étain, fer ou Cr(III), d'une part, avec b) des oxydes de vanadium, chrome (VI), molybdène, tungstène ou scandium, d'autre part, ou bien les oxydes mixtes sont des oxydes sulfatés ou phosphatés du groupe (a), lesdits oxydes mixtes étant calcinés, selon leur teneur en impuretés, à des températures comprises entre 450 et 800 °C.
PCT/EP1998/003507 1997-06-24 1998-06-10 Procede de fabrication de 4,4'-dihalogenodiphenylsulfone WO1998058907A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CA002283894A CA2283894A1 (fr) 1997-06-24 1998-06-10 Procede de fabrication de 4,4'-dihalogenodiphenylsulfone
AU84379/98A AU8437998A (en) 1997-06-24 1998-06-10 Method for producing 4,4' dihalogendiphenylsulfone
EP98934947A EP0993443A1 (fr) 1997-06-24 1998-06-10 Procede de fabrication de 4,4'-dihalogenodiphenylsulfone

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
DE19726806.4 1997-06-24
DE19726807.2 1997-06-24
DE1997126806 DE19726806A1 (de) 1997-06-24 1997-06-24 Verfahren zur Herstellung von 4,4'-Dihalogendiphenylsulfon
DE1997126805 DE19726805A1 (de) 1997-06-24 1997-06-24 Verfahren zur Herstellung von 4,4'-Dihalogendiphenylsulfon
DE1997126807 DE19726807A1 (de) 1997-06-24 1997-06-24 Verfahren zur Herstellung von 4,4'-Dihalogendiphenylsulfon
DE19726805.6 1997-06-24

Publications (1)

Publication Number Publication Date
WO1998058907A1 true WO1998058907A1 (fr) 1998-12-30

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PCT/EP1998/003507 WO1998058907A1 (fr) 1997-06-24 1998-06-10 Procede de fabrication de 4,4'-dihalogenodiphenylsulfone

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EP (1) EP0993443A1 (fr)
KR (1) KR20010020308A (fr)
AU (1) AU8437998A (fr)
CA (1) CA2283894A1 (fr)
WO (1) WO1998058907A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI289158B (en) 2000-08-10 2007-11-01 Oncolytics Biotech Inc Method of producing infectious reovirus
JP6585347B2 (ja) * 2011-12-15 2019-10-02 ソルベイ スペシャルティ ポリマーズ ユーエスエー， エルエルシー ジハロジアリールスルホンの異性体の混合物からハロアリール化合物を製造する方法
EP3858478A1 (fr) * 2020-01-31 2021-08-04 SCG Chemicals Co., Ltd. Catalyseurs et systèmes catalyseurs stables à forte sélectivité et leurs procédés d'utilisation

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB926291A (en) * 1958-07-25 1963-05-15 Philips Nv Improvements in or relating to processes for producing halogeno-diphenyl-sulphones
FR2541677A1 (fr) * 1981-08-31 1984-08-31 Mitsui Toatsu Chemicals Procede de preparation du chlorure de 4-chlorobenzene sulfonyle

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB926291A (en) * 1958-07-25 1963-05-15 Philips Nv Improvements in or relating to processes for producing halogeno-diphenyl-sulphones
FR2541677A1 (fr) * 1981-08-31 1984-08-31 Mitsui Toatsu Chemicals Procede de preparation du chlorure de 4-chlorobenzene sulfonyle

Also Published As

Publication number Publication date
KR20010020308A (ko) 2001-03-15
EP0993443A1 (fr) 2000-04-19
AU8437998A (en) 1999-01-04
CA2283894A1 (fr) 1998-12-30

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