GB2030566A - Preparation of 4,4'-dihydroxy- diphenylsulphone - Google Patents
Preparation of 4,4'-dihydroxy- diphenylsulphone Download PDFInfo
- Publication number
- GB2030566A GB2030566A GB7930573A GB7930573A GB2030566A GB 2030566 A GB2030566 A GB 2030566A GB 7930573 A GB7930573 A GB 7930573A GB 7930573 A GB7930573 A GB 7930573A GB 2030566 A GB2030566 A GB 2030566A
- Authority
- GB
- United Kingdom
- Prior art keywords
- dihydroxy
- diphenylsulphone
- mixture
- catalyst
- sulphuric acid
- 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.)
- Withdrawn
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/06—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The proportion of 4,4'-dihydroxy -diphenylsulphone in a mixture thereof with 2,4'-dihydroxy- diphenylsulphone is increased by heating the mixture with an added acidic catalyst in the presence of an organic solvent in which 4,4'- dihydroxy-diphenylsulphone is less soluble than 2,4'-dihydroxy- diphenylsulphone at the temperature employed. The 4,4'-isomer may be separated as a solid from the resultant slurry.
Description
SPECIFICATION
Preparation of 4,4' - dihydroxy - diphenylsulphone
This invention relates to the preparation of 4, 4' dihydroxy - diphenylsulphone.
It is known to prepare 4,4' - dihydroxy - diphenyl sulphone by reaction between phenol and sulphuric acid (the proportion of phenol being in excess of the stoichiometric proportion of 2 moles of phenol per mole of sulphuric acid) but the desired product is usually accompanied by an unacceptably high proportion of the isomeric 2,4' - dihydroxy - diphenyl sulphone as by-product.
In Japanese Patent Publication 51-98239 it has been proposed to carry outthe reaction between phenol and sulphuric acid in the presence of a solvent in which 4,4' - dihydroxy - diphenylsulphone is less soluble than 2,4'- dihydroxy- diphenylsulphone, the solvent being gradually evaporated from the reaction system. The 4,4' - dihydroxy isomer formed separates and, since the two isomers are in equilibrium, isomerization of the 2,4' - dihydroxy isomer proceeds.
This proposed method does, however, require careful control of the reaction conditions to ensure an appropriate balance between the rate of removal of the solvent and the rate of isomerization. Furthermore, the reaction product, after removal of the solvent, may be in the form of a rather intractable solid mass.
According to the present invention there is provided a process for increasing the proportion of 4,4' dihydroxy - diphenylsulphone in a mixture thereof with 2,4' - dihydroxy - diphenylsulphone which comprises heating the said mixture with an added acidic catalyst at a temperature in the range from 1 300C to 2000C in the presence of an organic solvent in which 4,4' - dihydroxy - diphenylsulphone is less soluble than 2,4' - dihydroxy - diphenylsulphone at the temperature employed.
This process yields relatively pure 4,4'-dihydroxydiphenylsulphone in the form of a slurry from which the solid product may readily be separated.
A wide range of solvents may be used in the process of the present invention as having the requisite inertness under the reaction conditions, being sufficiently high boiling to remain in the liquid phase and satisfying the requirement that 4,4' - dihydroxy diphenylsulphone is less soluble than 2,4' - dihyd roxy- diphenylsulphonetherein at the reaction temperature. The preferred solvents are chlorobenzenes, especially 1,2 - dichlorobenzene, but other solvents that may be used include, for example, aromatic hydrocarbons, other chlorinated aromatic hydrocarbons, hydrogenated (or partially hydrogenated) aromatic hydrocarbons and chlorinated aliphatic hydrocarbons.
A variety of acidic catalysts may be used in the process of the invention. It will be understood that the catalyst chosen, and the concentration thereof, will be such that there is substantially no reaction between the catalyst and the solvent or the other components of the reaction mixture. The catalyst must also be sufficiently involatile to remain in the reaction mixture under the conditions of temperature and pressure employed.
It is preferred that the catalyst is a relatively strong acid, for example an acid for which pKa is 4 or below.
Among inorganic acids, aqueous mineral acids are conveniently used, especially sulphuric acid. Suitable organic acids include fluorosulphonic acids, for example trifluoromethylsulphonic acid, CF3SO3H.
The proportion of catalyst to be added and the optimum proportion of water (if any) may readily be determined by simple trial. For example, when sulphuric acid is used it is convenient to use aqueous sulphuric acid containing at least 5% by weight of
H2SO4 (preferably from 10% to 90% by weight) but concentrated sulphuric acid is preferably not used this might cause sulphonation instead of simply acting as a catalyst. (The sulphonation of 2,4' - dihydroxy - diphenylsulphone is described in US Patent
No 3 366 692).
The 4,4' - dihydroxy - diphenylsulphone produced may be separated from the reaction mixture by conventional methods, for example filtration. The product thus obtained may already be of the required degree of purity but may, if desired, be further purified by known methods, for example by dissolution in aqueous sodium hydroxide solution followed by precipitation by acid.
The invention is illustrated by the following Examples.
EXAMPLE 7 The starting material was a mixture consisting of 91% by weight of 4,4' - dihydroxy - diphenylsulphone and 9% by weight of 2,4' - dihydroxy - diphenylsulphone.
1,2 - dichlorobenzene (100 g) and 50% w/w sulphuric acid (1.5 g) were added to 40 g of the starting material described and the resulting mixture was heated at 1 55,C for 1 hour. The mixture was then cooled and filtered, to yield 40 g of solid product: this was found by liquid chromatography to contain 1.8% by weight of 2,4' - dihydroxydiphenylsulphone, the remainder consisting of 4,4' - dihydroxy diphenylsulphone. The only other components detected were traces of the 2,2' - isomer and of a trihydroxy- diphenyldisulphone.
EXAMPLE2 TO4 The procedure of Example 1 was repeated, except that the concentration of H2SO4 and the period of heating were varied. The results obtained were as follows:
Example H2SO4 heating 2,4'-isomer %wlw period content
hours %w/w
2 10 3 2.2
3 50 3 1.6
4 90 1 2.4
Claims (5)
1. A process for increasing the proportion of 4,4' - dihydroxy - diphenylsulphone in a mixture thereof with 2,4' - dihydroxy- diphenylsulphone which comprises heating the said mixture with an added acidic catalyst at a temperature in the range from 130"C to 2000C in the presence of an organic solvent in which 4,4' - dihydroxydiphenylsulphone is less soluble than 2,4' - dihydroxy - diphenylsulphone at the temperature employed.
2. A process according to Claim 1 characterised in that the solvent is 1,2 - dichlorobenzene.
3. A process according to Claim 1 or Claim 2 characterised in that the catalyst is sulphuric acid.
4. A process according to Claim 3 characterised in that the catalyst is aqueous sulphuric acid containing from 10% to 90 /O by weight of H2SO4.
5. A process according to Claim 1 and substantially as described with reference to, and as shown in, any one of Examples 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7930573A GB2030566A (en) | 1978-09-15 | 1979-09-04 | Preparation of 4,4'-dihydroxy- diphenylsulphone |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7836979 | 1978-09-15 | ||
| GB7930573A GB2030566A (en) | 1978-09-15 | 1979-09-04 | Preparation of 4,4'-dihydroxy- diphenylsulphone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB2030566A true GB2030566A (en) | 1980-04-10 |
Family
ID=26268868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7930573A Withdrawn GB2030566A (en) | 1978-09-15 | 1979-09-04 | Preparation of 4,4'-dihydroxy- diphenylsulphone |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2030566A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1986006370A1 (en) * | 1985-04-19 | 1986-11-06 | Konishi Chemical Industry Co., Ltd. | Process for producing highly pure 4,4'-dihydroxydiphenyl sulfone |
| EP0364876A1 (en) * | 1988-10-19 | 1990-04-25 | BASF Aktiengesellschaft | Process for the preparation of Bis(4-hydroxyphenyl)sulfone |
| EP0380175A1 (en) * | 1989-01-27 | 1990-08-01 | Akzo Nobel N.V. | Process for forming 4,4'-dihydroxydiphenyl sulfone |
| US4996367A (en) * | 1989-12-20 | 1991-02-26 | Amoco Corporation | Process for making 4,4'-dihydroxydiphenyl sulfone |
| US5001270A (en) * | 1985-10-04 | 1991-03-19 | Amoco Corporation | Process for recovering 4,4' dihydroxydiphenyl sulfone from an isomer mixture |
| US5041677A (en) * | 1985-10-04 | 1991-08-20 | Amoco Corporation | Process for synthesizing 4,4'-dihydroxydiphenyl sulfone |
| US5189223A (en) * | 1989-09-14 | 1993-02-23 | Konishi Chemical Ind. Co., Ltd. | Process for preparation of 4,4'-dihydroxydiphenylsulfone |
| US5241121A (en) * | 1989-12-29 | 1993-08-31 | Konishi Chemical Ind. Co., Ltd. | Process for preparation of 4,4'-dihydroxydiphenylsulfone |
-
1979
- 1979-09-04 GB GB7930573A patent/GB2030566A/en not_active Withdrawn
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1986006370A1 (en) * | 1985-04-19 | 1986-11-06 | Konishi Chemical Industry Co., Ltd. | Process for producing highly pure 4,4'-dihydroxydiphenyl sulfone |
| GB2186569A (en) * | 1985-04-19 | 1987-08-19 | Konishi Chem Ind | Process for producing highly pure 4,4'-dihydroxydiphenyl sulfone |
| US4820831A (en) * | 1985-04-19 | 1989-04-11 | Konishi Chemical Industry Co., Ltd. | Process for preparing 4,4'-dihydroxydiphenyl sulfone having high purity |
| US5001270A (en) * | 1985-10-04 | 1991-03-19 | Amoco Corporation | Process for recovering 4,4' dihydroxydiphenyl sulfone from an isomer mixture |
| US5041677A (en) * | 1985-10-04 | 1991-08-20 | Amoco Corporation | Process for synthesizing 4,4'-dihydroxydiphenyl sulfone |
| EP0364876A1 (en) * | 1988-10-19 | 1990-04-25 | BASF Aktiengesellschaft | Process for the preparation of Bis(4-hydroxyphenyl)sulfone |
| US5059715A (en) * | 1988-10-19 | 1991-10-22 | Basf Aktiengesellschaft | Preparation of bis(4-hydroxyphenyl)sulfone |
| EP0380175A1 (en) * | 1989-01-27 | 1990-08-01 | Akzo Nobel N.V. | Process for forming 4,4'-dihydroxydiphenyl sulfone |
| US5189223A (en) * | 1989-09-14 | 1993-02-23 | Konishi Chemical Ind. Co., Ltd. | Process for preparation of 4,4'-dihydroxydiphenylsulfone |
| US4996367A (en) * | 1989-12-20 | 1991-02-26 | Amoco Corporation | Process for making 4,4'-dihydroxydiphenyl sulfone |
| US5241121A (en) * | 1989-12-29 | 1993-08-31 | Konishi Chemical Ind. Co., Ltd. | Process for preparation of 4,4'-dihydroxydiphenylsulfone |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |