DE2630600A1 - METHOD FOR MANUFACTURING DIARYL SULPHONES - Google Patents

Description

Folder: 24056 - Dr.Kn/La
(ICI CASE Dd. 28039)

IMPERIAL CHEMICAL INDUSTRIES LIT). ' London, UK

Process for the preparation of diarylsulfones

Priority: 7/11/75 - Great Britain

The invention "relates to a chemical process and in particular to a process for the preparation of diarylsulfones. c

Process for the preparation of diarylsulfones, in which organic Solvents are used are already known. The present invention makes it possible to use an aqueous Medium to use.

70 9815/1135

According to the invention, a method for production is thus used of diarylsulfones, which have a fitro substituent in at least have one of the 2 and 4 positions, proposed which is carried out by having a halobenz-ol with a Mitro substituents in at least one of the 2- and 4-positions with an arylsulfinic acid or a salt thereof in one aqueous medium in the presence of a phase transfer catalyst.

Examples of halobenzenes "in the Yer-.fahren according to the invention compounds of the formula:

z ²

where X is halogen, in particular chlorine or bromine, X- is Halogen, ITitro, cyano, alkyl, alkoxy, amino, alkylamino, Acylamino, sulfamoyl, mono- or dialkylsulfamoj? ·! or PIono- or diarylsulfamoyl, one of the symbols Z-. and Z for Nitro stands and the other of the symbols stands for hydrogen or Uitro and η stands for an integer from 0 to 3.

Specific examples of useful halobenzenes are 2-Mltrochlorobenzol, 2-Hitrobromobenzol, 2-ii.trofluorobenzol, 2-Kitro-QOdobenzol, 2,4-dinitrochlorobenzene (α-, ß- and y-porms), 2,4-dinitrobromobenzene, 2,3-dinitrochlorobenzene, 2,3-mnitrobromobenzene, ^ -Mtrochlorobenzene, 4-Uitrobromobenzol, 4-Mtrofluorobenzol, 4-ITitroiodobenzene, 2,6-dinitrochlorobenzene, 2,6-dinitrobromobenzene, 2,5 "-dinitrobromobenzene, 2,4,5-trinitro- chlorobenzene, 3,4-dinitrochlorobenzene, 2,3-dichloronitrobenzene, 2,4-dichloronitrobenzene, 2,5-dichloronitrobenzene, 2,6-dichloronitrobenzene, 2-M "itro-3-methoxychlorobenzene and 2-CyBnO - ^ - nitrochlorobenzene. .

- 2 -

70-981 5 / 1.1 3 5

Examples of arylsulfinic acids used in the invention Methods that can be used are compounds of the formula:

wherein the ring A optionally contains one or more alkyl, alkoxy, acylamino, .Fitrο or halogen substituents can carry. The SuI-fic acid can optionally be in salt form, in particular in the form of an alkali metal salt, very, especially sodium, Potassium or lithium salt., Or an ammonium, amine or other nitrogen base salt, x ^ ie e.g. in the form of a diphenylguanidine salt.

The term "phase transfer catalyst" as used herein " refers to a substance that promotes a reaction by causing a transition of a reactant and also a transition of oneself from a first phase to a second phase in which the reaction takes place, causes the phase transfer catalyst to be released back into the first phase for reuse will. Phase transfer catalysts are from E.V. Dehmlow in Angewandte Chemie (International Edition), Vol. 13 »STr. 3, Pp. 170-178, 1974.

Preferably the phase transfer catalyst used in the process of the invention is a quaternary one Salt of the formula:

R ¹
R ⁴ Jl ⁺ - R ² X-

709815 / 113g

where M is a pentavalent element of group Y of the periodic table, in particular nitrogen or phosphorus, R, P. "",

3 4- -

R and R stand for organic radicals and Σ for an anion

· "] P 3 ix.

stands. Organic radicals represented by R, R "", ~ 3r and R are optionally substituted alkyl, alkenyl, aryl, aralkyl and cycloalkyl radicals. Alternatively, minor

12 3 lists two of the Ea.dika.feR, R, R and R · connected to one another or condensed with one another, so that rings are formed. Examples of anions X ~ are, in particular, chloride, bromide and methosulphate ions. Double or multifunctional quaternary salts in which the formula (R ¹ R ² R ^ R ⁴ M ⁺ ) X "is pre-dissolved several times, - '· can also be used. The preferred phase transfer catalysts are quaternary ammonia

1 2 -5 4

nium salts in which R, R and Έ / are alkyl radicals and R is an alkyl or an aralkyl radical, the four radicals together having at least 12 and preferably 16-30 carbon atoms. Examples of suitable quaternary salts are cetyl-trimethyl-ammonium bromide, benzyl-tri-n-butyl-ammonium chloride, oetyl-trimethyl-ammonium chloride, oetyl-tri-npropyl-phosphonium bromide, octyl-tributyl-ammonium bromide, tetrabutyl-ammonium bromide, {erioctyl-ammonium bromide, {erioctyl-ammonium bromide -ammonium chloride, benzyldimethyl-lauryl-ammonium chloride and tetrabutyl-ammonium sulfate.

If necessary, the quaternary salt can be formed in situ, for example by introducing a tertiary amine and an alkylating agent into the reaction mixture.

Other phase transfer catalysts which can be used _s are the crown ethers (makroeyclische polyether) that is described in Journal of the American Chemical Society, Vol. 89 _{9 0} SS from 7017 to 7036, 1967 ₅ of GOJ ₀ Pedersen

The lease transfer catalyst is used in a catally effective amount ₉ and is suitably used in an amount of 1 to 50 g per gram mol of aryl sulfinic acid used in the reaction mixture.

The process according to the invention can expediently be carried out by using the halobenzene or arylsulfinic acid or the salt thereof and the phase transfer catalyst in the presence of water and optionally in the presence of an organic one Solvents such as ethanol, dimethylformamide, dimethyl sulfoxide or ethoxyethanol. The temperature is adjusted so that the halobenzene is in a liquid Phase is located. This depends on the melting point of the halobenzene and also on whether a solvent is used. the The amount of water can be varied within a wide range

(3rd S / T
den and can only be 50 ml per gramol / reactant. The reaction can be preferably carried out at atmospheric pressure, in which case appropriate amount to reaction temperatures 40-110 ⁰ C. Alternatively, the reaction can be carried out up to 250 ⁰ C in an autoclave at temperatures.

Any of the reactants can be used in excess. However, it is preferred to use an excess of the halobenzene to use, which at the end of the reaction expediently by steam distillation together with a possibly present Solvent can be removed. The diarylsulfone product can optionally be isolated and purified in the usual way, for example by filtration and crystallization.

The Hltrodiarylsulfone obtained by the process according to the invention can be converted into aminodiarylsulfones, which as Diazo components useful in the manufacture of azo dyes are.

The invention is illustrated in more detail by the following examples, in which all parts are expressed by weight,

example 1

A G-amiscli from 8.2 parts of sodium benzenesulfine.t _s 35 parts

Ω ; -. ΐίϊ; ; Τ:

2-Eitrochlorobenzene, 5 parts of water iind 0.5 parts of cetyl • trimethylammonium bromide is stirred at 100-1O5 ° C for 18 hours.
Thin-layer chromatography shows that the reaction is then completely over. 50 parts of hot water (50 ⁰ C) are then added to the mixture, after which excess 2-Mtrochiο-robenzöl is removed by steam distillation. The product, which separates out in the form of granular crystals during the distillation, is filtered off and dried. The product is identical to 2-Fitrodiphenylsulfon, which was prepared by previously known processes
is.

If the method omitting the cetyl-trimethyl-ammonium broirtide is repeated, then virtually no reaction can be detected by thin layer chromatography.

In a similar manner, the halobenzenes listed in column 1 of Table 1 were mixed with the alkali metal salts
of the substituted sulfinic acids listed in column 2
are implemented. The corresponding sulfones were obtained in this way. The phase change catalyst used in each reaction is given in column 3.

709816/1138

Table 1

at
game 1 2 5 2 ?. , 4-dinitrochloro-
benzene p-toluenesulfine
acid Benzyl— "bri — n—
butyl ammonium
chloride 3 2,5-binitrochloro-
benzene Benzolsnlf in
acid Oetyl-trim tb.yl-
amiaonluniciil ο pid Δ. 2- cyan ο-4 ~ nitro-
chlorobenzene 3-acetamido
benz-oleulfine-
acid Cetyl-trl-n-
propyl-pho spho-
nium bromide ς 2,4-Dinltrobromo-
benzene 2-? Ethoxybenzene-
sulfinic acid Oe tyl-trimethyl-
ammonium chloride 6th I! 2.5 dichloro
b ens ο1sulfine-
acid I! 7th 2,5-dinitrobromo
benzene 2-Brο mobenzol-
sulfinic acid Benzyl-trl-n-
butyl ammonium
chloride 8th I! 4 — Ac etamidob en-
zolsulfin
acid e Octyl tributyl
ammonium bromide 9 2-Hitrocliloro
benzene It Cetyl trimethyl
ammonium chloride 10 It 4-Wethoxyben-
solsulfinic acid It 11 I! p-toluenesulfine
acid e Te trab utyl -ammo - »
nium bromide

709815/113 5.

Example 12

fi ^ t ■ - - • <■ iJ / '-

A Geraisch aue 33 parts HatrJum-benzol-sulfinat, 31? 5 parts of HitxOcliloro "ben", ol and 0.5 parts of cetyl trimethyl ammonium bromide in 290 parts of water are heated in an autoclave to 140-150 ⁰ O for 24 hours with effective stirring 2-liter-nitrochlorobenzene is then removed by steam distillation. The product which separates out during the steam distillation is filtered off, washed with water and dried, 35 S (8.7 '% of theory) of 2-nitrod.iphenylsulfone being formed.

When the process in the absence of cetyl trimethyl ammonium bromide is carried out., then practically no reaction takes place.

709815/1135 ORIGINAL BATHROOM

Claims (1)

Process for the preparation of oiarylsulfones which have a Uitro substituents in at least one of the 2- and 4-positions contain, characterized in that a halobenzene which has a Hitrosubstituenten in at least one contains the 2- and 4-positions, mit.ein arylsulfinic acid or a salt thereof in an aqueous medium in the presence of a phase transfer catalyst. Process according to Claim 1, characterized in that a compound of the formula: R ¹ _R A _ I ₁ ⁺ - R ²
r3 is used, where M is a pentavalent element of the 1 2 ⁷ I 4 Group V of the periodic table stands, R, R, R "and R stand for organic radicals and X ~ stands for an anion. ■ o 3. The method according to claim 2, characterized in that H represents nitrogen or phosphorus. 4. The method according to claim 3, characterized in that M stands for nitrogen, r / ¹ , R ² and R ^ for alkyl radicals ste- Zl hen and R is an alkyl or aralkyl radical, where the four radicals together contain at least 12 carbon atoms. 5. The method according to claim 4-, characterized in that R, ο 7) Zl
τ ?. ", R- 'and R' together contain 16-30 carbon atoms. β. Method according to one of the preceding claims, characterized in that characterized in that the phase transfer catalyst is used in an amount of 1 to 50 grams per gram mole of arylsulfinic acid will. 709815/1135
ORIGINAL BATHROOM *