Bis- 4-chlorophenyl -sulfone

Bis-(4-chlorophenyl)-sulfone is an important intermediate, which is used mainly for the preparation of aromatic poly(sulfone)s and for the synthesis of bis-(aminophenyl)-sulfone. This compound is required both for the therapy of leprosy and for curing epoxy resins. 

The most well-known method for the preparation of bis-(4-chloro-phenylj-sulfone is the Friedel-Crafts reaction of 4-chlorobenzenesulfonyl chloride with chlorobenzene, the catalyst used, for example, iron(III) chlor- 

However, iron(III) chloride also acts as a chlorinating agent for chlorobenzene at this temperature. Therefore, considerable amounts of dichlorobenzenes are formed as byproducts. Dichlorobenzenes can react with chlorobenzenesulfonyl chloride to give undesirable sulfones. 

If the reaction is carried out as a single-stage reaction starting from chlorobenzene, without isolation of the intermediate chlorobenzenesulfonyl chloride, care must be taken to ensure that sulfonic acid, thionyl chloride and sulfur chlorides, as impurities in the thionyl chloride, are no longer present in the reaction mixture, since the free sulfonic acid causes deactivation of the catalyst, and thionyl chloride and sulfur chlorides Ukewise lead to undesirable byproducts. A further difficulty is that iVA -dimethyl-formamide is required for complete conversion of chlorobenzenesulfonic acid with thionyl chloride into the corresponding sulfonyl chloride, carcinogenic A,A-dimethylcarbamyl chloride being formed as a byproduct. 

Another synthesis route for bis-(4-chlorophenyl)-sidfone is the reaction of chlorobenzene and chlorobenzenesulfonic acid. At 220-260°C at an elevated pressure of 1.7 bar, bis-(4-chlorophenyl)-sulfone is obtained in a good yield. 

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An example of a sulfite ester made from thionyl chloride is the commercial iasecticide endosulfan [115-29-7]. A stepwise reaction of thionyl chloride with two different alcohols yields the commercial miticide, propaigite [2312-35-8] (189). Thionyl chloride also has appHcations as a co-reactant ia sulfonations and chlorosulfonations. A patent describes the use of thionyl chloride ia the preparation of a key iatermediate, bis(4-chlorophenyl) sulfone [80-07-9] which is used to make a commercial polysulfone engineering thermoplastic (see Polymers CONTAINING SULFUR, POLYSULFONe) (190). The sulfone group is derived from chlorosulfonic acid the thionyl chloride may be considered a co-reactant which removes water (see Sulfolanes and sulfones). 

Jomndsdottir, H. Norstrom, K. Olsson, M. Pham-Tuan, H. Hiihnerfuss, H. Bignert, A. Bergman, A, Temporal trend of bis(4-chlorophenyl) sulfone, methylsulfonyl-DDE and -PCBs in Baltic guillemot Uria aalge) egg 1971-2001 A comparison to 4,4 -DDE and PCB trends Environ. Pollut. 2006, 141, 226-237. 

Larsson, C. Norstrom, K. Athanansiadis, I. Bignert, A. Konig, W.A. Bergman, A, Enantiomeric specificity of methylsulfonyl-PCBs and distribution of bis(4-chlorophenyl) sulfone, PCB, and DDE methyl sulfones in grey seal tissues Environ. ScL TechnoL 2004, 38, 4950 955. 

TCPM is reported in samples from areas from all over the world. A reason for this ubiquitous occurrence may be the presence of the 4-chlorophenyl rings in the compound, which are also found in p,p -DDT and its metabolites p,p -DDD and p,p -DDE, which are also very persistent contaminants. This structure is also found in bis(4-chlorophenyl) sulfone, which was recently reported as a new persistent contaminant [14]. The 4-chlorophenyl structure is apparently very resistant to transformation in the environment. Only in Mediterranean fish samples were TCPM and TCPMe not detected at a level of 1 pg/kg lipid weight. TCPM concentrations on a lipid weight basis decrease from 180 pg/kg to 360 pg/kg in eel from the river Rhine delta, to 40 pg/kg in cod liver from the southern North Sea, and to 6 pg/kg in cod liver from the northern North Sea (Table 2). This suggests a relationship between high TCPM concentrations and densely populated, industrialized areas. High TCPM concentrations in samples from the Baltic Sea and Lake Ontario and low TCPM concentrations in samples from Antarctica confirm this hypothesis. 

The reaction of bis(4-chlorophenyl)sulfone with the anhydrous dialkali salt of a,a -bis(4-hydroxyphenyl)-p-diisopropyl benzene, which is dissolved in an aprotic solvent, leads to a new heat-resistant polyarylsulfone. A general discussion of monomer and polymer preparation is given as well as physical and mechanical properties of this polyarylsulfone. 

The polyarylsulfone thermoplastic exhibits essentially the same heat resistance of the polyarylstdfone based on bis-(4-chlorophenyl)sulfone and 2,2-bis(4-hydroxyphenyl)pro-pane, along with the added plus of a lower melt viscosity at equivalent processing temperatures. The flow improvement is demonstrated by comparison with Brabender data, injection-molding conditions, and melt-viscosity data. 

Jn recent years, there has been a considerable amount of interest in high-molecular-weight polyarylsulfone polymers (1-3). These polymeric materials possess heat-deflection temperatures of 165°-260°C plus excellent thermal stability at the high processing temperatures required. This paper deals with the synthesis and the physical and mechanical properties of a new heat-resistant polyarylsulfone. This new polyarylsulfone thermoplastic exhibits a significant reduction in apparent (melt) viscosity with only a slight reduction in heat deflection temperature when compared with the polyarylsulfone based on bis(4-chlorophenyl)sulfone and 2,2-bis (4-hydroxyphenyl) propane. 

Monomers. Bis ( 4-chlorophenyl ) sulfone. We prepared bis (4-chlorophenyl)sulfone (I in Reaction 1) by dropwise addition of chloro-sulfonic acid (0.4 mole) to chlorobenzene (0.2 mole) at 0°C. One hour after the chlorosulfonic acid addition was completed, an additional quantity of chlorobenzene (0.16 mole) was added to the cold solution. 

The reaction mixture was allowed to warm gradually to 50°C. The reaction was quenched by pouring into ice water. The aqueous suspension was heated to hydrolyze p-chlorobenzenesulfonyl chloride (II) to the water-soluble sulfonic acid. The desired product was filtered and washed with water until essentially neutral. Bis (4-chlorophenyl) sulfone was purified by recrystallization from benzene—m.p. 145°-147°C (4). Extremely low yields were obtained by this process. By contrast, yields in excess of 90% have been reported in processes that involve the reaction of chlorobenzene with sulfur trioxide and dimethyl or diethyl sulfate (5, 6). 

Polymerization. Typically, the dihydric phenol (1 mole) and aqueous alkali metal hydroxide (2 moles) are mixed under an inert atmosphere in sulfolane and benzene. The water from the aqueous solution plus metal phenoxide formation is removed by distillation of a benzene-water azeotrope between 110° and 140°C. After water removal has been completed, the excess benzene is distilled off, the anhydrous salt in sulfolane cooled to 70°-80°C, and bis(4-chlorophenyl)-sulfone (I) added. The temperature is increased gradually to 200°C and held for four to five hours. Methyl chloride is bubbled in at the end of the polymerization to convert any terminal phenoxide groups to methyl ethers (10). 

Polymer Evaluation. Physical properties, melt-viscosity data, and gel permeation chromatography data of our polyarylsulfone IV and the polyarylsulfone V based on bis(4-chlorophenyl)sulfone and 2,2-bis(4-hydroxyphenyl) propane (11) are listed ip Tables I through IV and Figures 1 through 3. 

Beilstein Handbook Reference) 4,4 -Dichlorodiphenyl sulfone AI3-01386 AI3-02901 Benzene, 1,1 -sulfonylbis(4-ohioro- Bis(4-chlorophenyl) sulfone Bis(4-chlorophenyl) sulphone Bis(p-chlorophenyl) sulfone BRN 2052955 Di-p-chlorophenyl sulfone EINECS 201-247-9 HSDB 5233 NSC... 

Polysulfones Polysulfones are aromatic PEs made usually by the reaction of bisphenol A and bis (4-chlorophenyl) sulfone in a nucleophilic substitution condensation reaction. The first polysulfones produced by Union Carbide in the early 1960s involved the reaction of bisphenol with and bis(4-chlorophenyl) sulfone in the presence of an alkali base (NaOH, KOH, and K carbonate) in a dipolar aprotic solvent such as NMP, DMSO, sulfolane, or dimethyl acetamide [78], Typical temperatures are in the range of 130-160 °C. The reaction of the base with bis A generates water, which must be removed. 

Further, bis-(4-chlorophenyl)-sulfone can be prepared by heating a mixture of chlorobenzene and sulfuric acid to 200-250°C. The water formed in the course of the reaction is removed by azeotropic distillation. The process is conducted at a pressure of 4-5 bar. The addition of catalytic amounts of boric acid or trifluoromethanesulfonic acid reduces the reaction time considerably. 

Bis-(chloromethyl)-l,3,4-oxadiazole, 337, 338 Bis-(4-chlorophenyl)-sulfone, 241, 242, 291 Bis-(2,4-di-fert-butylphenyl)-pentaerythritol diphosphite, 363... 

Lcolivet. C. Sougotti, M. Delugeard, D. Beaufils. S. High resolution Raman study of the soft mode in the incommensurate bis(4-chlorophenyl sulfone) J. Phys. 1 (France) 1994.. 1451. 

Stumpp M, Neumann P, Eilingsfeld H. Preparation of bis-(4-chlorophenyl) sulfone. US patent 4983773, assigned to BASF Aktiengesellschaft, Ludwigshafen, DE 1991. 

Random copoly(p-phenylene sulfide sulfone/ketone)s were easily prepared in high yield ( 95-99%) by the solution (NMP) condensation of sodium hydrosulfide (NaSH) with bis(4-chlorophenyl) sulfone (4,4 -dichlorodiphenyl sulfone) [80-07-9] and 4,4 -dichlorobenzophenone [98-98-2]. Copolymers with sulfone/ketone molar ratios > 25 75 were amorphous, whereas those with ratios < 25 75 were crystalline. These materials form tough, creaseable films and exhibit a linear increase in the Tg from 144 to 215°C, with increasing sulfone content (62). 

Method of synthesis - polysulfone is produced by the reaction of a bisphenol A and bis(4-chlorophenyl)sulfone ... 

This concept has been successfully applied to the synthesis of a,co-dicarboxyoligoesters, a,cu-dicarboxyoligoamides, and of phenoplasts and aminoplasts having reactive end groups. It has also been applied to the preparation of epoxy resins and a,to-diphenol carbonates. As shown in equation (58) a, 0-dihydroxy(PSU) can be prepared by reacting excess of the potassium salt of bisphenol A with bis(4-chlorophenyl)sulfone in either anhydrous DMSO (KOH or NaOH as base) °" or dimethylacetamide (K2CO3 as base). ... 

From these biphenols, polymers 28 with these different substituents on the imide nitrogen have been synthesized by reaction of the monomers with activated dihalides. The N-phenyl substituted biphenol, for example, gives a poIy(ether sulfone) by reaction with bis(4-chlorophenyl sulfone) which has a Tg of 310 C which has outstanding thermooxidatve stability... 

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