Indi an Journa l of Chemistry Vol. 408, March 200 1, pp . 237-239 Note An efficient a nd novel method for the sy nthesi s of aromatic sulfones under solvent- free conditions Abdol R Hajipour*, Shadpour E Ma ll akpour* & G Imanzadch Co ll ege of Chemistry, Is fa han Univers it y of Technology, Isfahan , Isfahan 84156 IR. IRAN , Email: haji (a • cc. iut.a c. ir Received 2 7 August 1999; accept ed (r evised) 26 July 2000 A manipulative simple and rap id reaction of arcnsulfonyl chl oride wi th aromatic hydrocarbons is described. The react i on is co ndu ct ed und er Friedei-Crafts conditions in th e absences of so lve nt usi ng aluminium chloride as catalysts. The mo st prac tical laboratory method of preparing aryl sulfones is a Friedei-Crafts method emp lo ying a sulfonyl chloride, aromatic hydrocarbon and aluminium chl orid e catalysts. 1 Other methods including th e oxidation of sulfides and sulfoxid es to th e corresponding sulfone s, 2 di splacement rea ction between sodium sulfinate and ary l halides, 3 reaction of Grignard reagent with aryl-p-toluene sulfinates, 4 react ion of arom atic sulfonic anhyd rid es with aromatic hydrocarbons in th e presence aluminium chloride catalysts 5 and reaction of aryl sulfonic acids with aromatic hydrocarbons in a polyphosphoric acid medium , 6 but many of these either give low yields, ha ve limitation, or require special tec hniqu es. 7 Beckurt and Otto 8 reported that no reaction occurred between benzenesulfonyl chloride and bromoben ze ne in the presence of aluminum chloride, both compounds were recoverd, although chlorobezene gave the corresponing sulfone in 87% yie ld . Heterogen eo us re actions that are facilitated by supported reagents on various solid inorga nic surfaces have received attention in recent years 9 - 11 • The advantages of these methods over conventional homogenous reactions are that they provide greater se lectivity, en hanced rea ction rates, cleaner products and manipulative simplicit y. In continuation of our ongo in g program to develop environmentally beni gn methods us in g solid supports, 12 - 16 we now wish to re port an extreme ly convenient synth es is of aromatic sulfones from readily available arensulfonyl chloride with aromat ic hydrocarbons in th e presence of alumin ium chloride as ca talysts under solid phase conditions (Scheme I). The process in it s entirety involves a simple mi xing of sulfonyl chlorides 1 and aro matic hydrocarbons 2 in the presence of aluminium chloride as catalysts in a mortar and grinding th e mixture for the time specified in Tabl e I. The yields of the reactions are hi gh (50-91 %) and the reaction tim es are exceedingly short (2-25 min ). To the best of our knowledge this technique for the preparation of aromatic sulfones is completely no ve l and has not bee n reported in the lit eratur e. The purities of products 3 were determined by 1 H NMR, IR , melting point and TLC analyses. The substitution effects ha ve been studi ed in th ese reactions (Table 1 ). According to data li sted in Table I, it is clear th at electron donating groups have increased the reaction rate as well as re ac tion yie ld s (Table I, entries l-12). On the other hand electron withdrawing groups have decreased yields and increa se d rea ction time (Table I, entries 13-18). When more than one moderate electron withdrawing groups or one strong withdrawing group are on the aromatic hydrocarb on 2 the reaction does not take place at all, even at 80 °C after 30 min grinding of the reaction mixture (Table I, entries 20-21). When a group such as N.N- dimethylamine was located on the aromatic hydrocarbon 2, although this gro up is an excellent electron releasing group, but th e reaction do es not occur at all , even at 80 °C after 30 min grinding of the reaction mixture (Tab le I, entry 22). This could be exp lain ed in tenns of complex formation between thi s group and aluminium chloride, which retards the reaction. In conclus ion we report here an efficient and novel method for preparation of aromatic su lf one und er solvent-free conditions using su lf onyl ch lorides 1 and aromatic hydrocarbons 2 m the presence of 0 II Ar-S-Cl + Ar'H II 0 1 2 0 II Ar-S-Ar ' II 0 3 Ar :a= G- Ar' = Ar}A Scheme I
Transcript
Indian Journa l of Chemistry Vol. 408 , March 200 1, pp. 237-239
Note
An efficient and novel method for the synthesis of aromatic sulfones under solvent
free conditions
Abdol R Hajipour* , Shadpour E Mallakpour* & G Imanzadch
Co llege of Chemistry, Isfa han University of Technology, Isfahan , Isfahan 84156
IR. IRAN, Email: haji (a •cc. iut.ac. ir
Received 2 7 August 1999; accepted (revised) 26 July 2000
A manipulative simple and rap id reaction of arcnsulfonyl chl oride wi th aromatic hydrocarbons is described . The react ion is conducted under Friedei-Crafts conditions in the absences of so lvent usi ng aluminium chloride as catalysts.
The most practical laboratory method of preparing aryl sulfones is a Friedei-Crafts method employing a sulfonyl chloride, aromatic hydrocarbon and aluminium chloride catalysts. 1 Other methods including the oxidation of sulfides and sulfoxides to the corresponding sulfones,2 displacement reaction between sodium sulfinate and ary l halides,3 reaction of Grignard reagent with aryl-p-toluene sulfinates,4
reaction of aromatic sulfonic anhyd rides with aromatic hydrocarbons in the presence aluminium chloride catalysts5 and reaction of aryl sulfonic acids with aromatic hydrocarbons in a polyphosphoric acid medium,6 but many of these either give low yields, have limitation, or require special techniques. 7
Beckurt and Otto8 reported that no reaction occurred between benzenesulfonyl chloride and bromobenzene in the presence of aluminum chloride, both compounds were recoverd, although chlorobezene gave the corresponing sulfone in 87% yield.
Heterogeneous reactions that are facilitated by supported reagents on various solid inorganic surfaces have received attention in recent years9
-11
• The advantages of these methods over conventional homogenous reactions are that they provide greater selectivity, enhanced reaction rates, cleaner products and manipulative simplicity. In continuation of our ongoing program to develop environmentally benign methods using solid supports, 12
-16 we now wish to
report an extremely convenient synthesis of aromatic sulfones from readily available arensulfony l chloride with aromat ic hydrocarbons in the presence of alumin ium chloride as catalysts under solid phase
conditions (Scheme I). The process in its entirety involves a simple mi xing of sulfonyl chlorides 1 and aromatic hydrocarbons 2 in the presence of alumin ium chloride as catalysts in a mortar and grinding the mixture for the time specified in Table I. The yields of the reactions are hi gh (50-91 %) and the reaction times are exceedingly short (2-25 min). To the best of our knowledge this technique for the preparation of aromatic sulfones is completely novel and has not been reported in the literature. The purities of products 3 were determined by 1 H NMR, IR, melting point and TLC analyses.
The substitution effects have been studi ed in these reactions (Table 1). According to data li sted in Table I, it is clear that electron donating groups have increased the reaction rate as well as reaction yie lds (Table I, entries l-12). On the other hand electron withdrawing groups have decreased yields and increased reaction time (Table I, entries 13-18). When more than one moderate electron withdrawing groups or one strong withdrawing group are on the aromatic hydrocarbon 2 the reaction does not take place at all, even at 80°C after 30 min grinding of the reaction mixture (Table I, entries 20-21). When a group such as N.Ndimethylamine was located on the aromatic hydrocarbon 2, although this group is an excellent electron releasing group, but the reaction does not occur at all , even at 80°C after 30 min grinding of the reaction mixture (Table I, entry 22). This could be exp lained in tenns of complex formation between thi s group and aluminium chloride, which retards the reaction.
In conclusion we report here an efficient and novel method for preparation of aromatic su lfone under solvent-free conditions using su lfonyl ch lorides 1 and aromatic hydrocarbons 2 m the presence of
0 II
Ar-S-Cl + Ar'H II 0 1 2
0 II
Ar-S-Ar' II 0 3
Ar :a=G- b=~-o-Ar' = Ar}A
Scheme I
238 IND IAN J CI-IEM., SEC 13, MARCH 200 1
Table I-React ion of arensul fonyl chl ori de with aromatic hydrocarbons
Ent ry Ar Ar' H Products• Peri od Yield mp oc Time (%)b (lit. 5. 6. 17. 18)
19 C6H5 3-bromotoluene C61-15S02C6H3-2-Me-4-Br 5 60 mi xture
C61-15S02C61-13-2-Br-4-Me
20 4-Cf-13C61-14 nitroben zene 30 0
21 4-Cl-13C61-14 2,4-di bromobenzene 30 0
22 4-CH3C61-14 N,N-dimethylaniline 30 0
•>confirmed by comparison with au thentic sample (IR, TLC and NMR). b)Y ield of isolated pure product
alumi nium chloride as catalysts. Thi s methodology is superior from view of yield, reaction time and easier work-up to the reported methods . In this methodology the products are pure and do not need any purification.
Experimental Section All prod ucts were identi fied by compari son with an
authentic sample5·6 (JR, NMR, and mp). All mps were
taken on a Gallenkamp melting apparatus and are uncorrected. 1 H NMR spectra were recorded on a Vari an EM-390 NMR Spectrometer operating at 90 MH z. The spectra were measured in CDCI3 unless otherwise stated, relati ve to TMS (0.00 ppm).
remain ing sul fo nyl chloride and extracted with ether (2x20 mL). The solvent was evaporated under red uced pressure at room temperature to give the pure product. In the cases of entries 14, 18 and 19 in Table I , we tri ed to purify the crude product by column chromatography on sili ca gel using hexane/ethyl acetate (90: 1 0) as eluent, but the separati on of two isomers was not success ful.
General procedure. A mortar was charged with the sulfonyl chloride (1 mmole), and powdered anhyd. alumi nium chloride (2 mmole) under efficient hood. The reaction mixture was ground with a pestle in the mortar fo r 1 min , then aromatic hydrocarbon ( I mmole) was added to the reacti on mixture. The reaction mixture was grou nd till TLC shows no
Acknowledgement Parti al support of this work by the Isfahan ,
University of Technology Research Council is gratefull y acknowledged.
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