Organic compounds -- part of the class 532-570 series – Organic compounds – Halogen containing
Reexamination Certificate
2001-12-12
2002-12-10
Siegel, Alan (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Halogen containing
Reexamination Certificate
active
06492569
ABSTRACT:
The present invention relates to a process for the preparation of compounds having the formula (I) C
6
F
4
HX wherein X is Br or Cl.
More specifically, the present invention relates to a method for the preparation of 1-bromo-2,3,4,5-tetrafluorobenzene.
The compounds having the formula (I) are useful intermediates for the synthesis, for example, of fluorinated fluorenes which are used as polymerization cocatalysts of &agr;-olefins.
The preparation of compounds having the formula (I) by reacting the halogen with tetrafluorobenzene in oleum (SO
3
in sulfuric acid), is known in the art.
For example the patent U.S. Pat. No. 3,424,804 describes a synthesis method which comprises (i) a first step in which tetrafluorobenzene is reacted with bromine in oleum, to produce a mixture containing monobromo- and dibromotetrafluorobenzene, and (ii) a second step in which the dibromotetrafluorobenzene coming from the first step is reduced with zinc powder, in glacial acetic acid, to give the compound monobromotetrafluorobenzene.
Operating according to this process a final yield of the compound monobromotetrafluorobenzene of 58% is obtained.
Bourdon et al. (Tetrahedron, 22, 2541-2549, 1966) describe a method for the preparation of tetrafluorobromobenzene which consists in reacting tetrafluorobenzene with bromine at 0° C., in oleum at 20% in the presence of AlBr
3
1%.
The halogenation reaction is a typical substitution reaction at the aromatic ring and is characterized by the co-presence of secondary reactions, parallel and subsequent to the main reaction (monohalogenation). The most important of these secondary reactions are the subsequent halogenations of the monohalogenation product, with the formation of dihalogenated products.
In the case of the bromination of tetrafluorobenzene with bromine therefore, more or less significant quantities of dibromotetrafluorobenzene are formed, together with the main product.
Other by-products, such as sulfuric derivatives of tetrafluorobenzene soluble in water, cannot on the other hand be recovered and their formation must be limited to reduce specific consumptions of this compound, which is extremely costly, and raise the process yield.
These known processes therefore substantially present the drawbacks deriving from problems relating to corrosion and low yields and selectivity of the product in question.
The objective of the present invention is to obtain compounds having the formula (I) with high yields and selectivities, by means of a process which is simple, economic and easy to effect on an industrial scale and which does not have the disadvantages of the processes of the known art.
It has now been found that this target can be reached if the reaction between tetrafluorobenzene and halogen is carried out in the presence of a Lewis acid catalyst and in the absence of a solvent of the oleum type.
The process of the present invention allows the useful reaction product to be obtained with high yields and selectivities.
In accordance with this, the present invention relates to a method for the preparation of compounds having the formula (I) C
6
F
4
HX wherein X is Br or Cl, which comprises:
(a) reacting tetrafluorobenzene with the halogen with a ratio ranging from 0.5 to 1 mole per mole of tetrafluorobenzene, in the presence of a Lewis acid catalyst, and
(b) recovering the compound having the formula (I) from the reaction mixture.
Catalysts suitable for the purposes of the present invention generally consist of Lewis acids such as halides of aluminum, tin, zinc, iron, titanium and zirconium. Among aluminum compounds, aluminum chloride is preferably used.
The quantity of catalyst can vary from 0.1 to 2.0% by weight, preferably from 0.5 to 1.0% by weight, per 100 g of tetrafluorobenzene.
The reaction temperatures can vary from 0 to.50° C.
The reaction time is selected in relation to the temperature; however, reaction times ranging from 0.5 to 6 hours are sufficient.
According to a preferred embodiment of the process of the present invention, the reaction between tetrafluorobenzene and the halogen is carried out in the presence of the catalyst, at 10-15° C. until hydrohalogen acid begins to develop. The temperature is then brought to values of 2 to 3° C. and, when the acid development decreases, the reaction mixture is again raised to 10-15° C.
The reaction is generally carried out at atmospheric pressure.
The process according to the present invention can be carried out batchwise, in continuous or semi-continuous.
At the end of the reaction, the compound having the formula (I) is recovered using the normal separation techniques. For example. the compound (I) can be isolated by fractionated distillation.
Operating according to the method of the present invention, high yields and selectivities of the useful reaction product can be obtained in a single step, in short times and with a low production of dihalogentetrafluorobenzene.
The following examples, whose sole purpose is to describe the present invention in greater detail, should in no way be considered as limiting the scope of the invention itself.
REFERENCES:
patent: 3424804 (1969-01-01), Tilney-Bassett
patent: 5847241 (1998-12-01), Oren
patent: 6307113 (2001-10-01), Sabahi
J. Burdon et al.: “Aromatic polyfluoro compounds—XXXIV Nucleophilic replacement reactions of some tetrafluorohalogenbenzenes”vol. 22, 1966, pp. 2541-2549 cited in the application p. 2545.
Borsotti Giampietro
Santi Roberto
Sommazzi Anna
Enichem S.p.A.
Siegel Alan
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