Oxidation process

Details Oxidation process Oxidation process

1998-09-08

2001-11-27

Killos, Paul J. (Department: 1623)

Organic compounds -- part of the class 532-570 series

Organic compounds

Oxygen containing

C568S716000, C568S797000, C568S803000

Reexamination Certificate

active

06323377

ABSTRACT:

The present invention concerns the selective oxidation of 1,4-dichlorobenzene to 2,5-dichlorophenol.
U.S. Pat. No. 4,529,824 describes in general certain complexes of vanadium, niobium and tantalum and their use in hydroxylating aromatic hydrocarbons either as reactant or catalyst. Additionally, Moiseeva et al. Kinet. Katal 29(4), 970-4 (1988) describe oxidation of benzene with vanadium compounds albeit not selectively for phenol (oxidation proceeds at least in part to quinone).
It has now surprisingly been found that oxidation of 1,4-dichlorobenzene to 2,5-dichlorophenol can be effected with high yield and selectivity when carried out in the presence of certain metal derivatives and in the presence of formic or an alkanoic acid.
The present invention therefore provides a process for the preparation of 2,5-dichlorophenol which comprises selectively oxidizing 1,4-dichlorobenzene using an oxidizing agent and a peroxo-, hydroperoxo-, superoxo- or alkylperoxo-metal species wherein said metal is selected from scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, selenium, tellurium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, zinc, aluminum, gallium, indium, tin, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, and uranium or mixtures thereof in the presence of an acid selected from formic or an alkanoic acid.
The oxidation may be effected using an oxidation agent. Suitable oxidation agents included organic peroxides such as peroxycarboxylic acids, RCO
3
H, alkyl hydroperoxides, ROOH, and dialkylperoxides, ROOR, for example peroxyacetic acid, peroxybenzoic acid, peroxyformic acid, t-butyl hydroperoxide, and di-t-butylperoxide and inorganic peroxides such as peroxydisulfuric acid. The preferred peroxide for use in the invention however, is hydrogen peroxide, especially in aqueous solution. The present process can be carried out at dilutions of 3% to 90% with almost complete utilization of H
2
O
2
and quantitive yields. However, ca 50% aqueous H
2
O
2
is preferred. The proportions of H
2
O
2
to 1,4-dichlorobenzene may vary between 0.2 and 5, e.g. between 0.5 and 2. It has been determined that particularly high efficiency may be achieved using approximately equimolar amounts of H
2
O
2
and 1,4-dichlorobenzene, e.g. ca 0.9 to ca 1.1 molar proportion of H
2
O
2
per mole of 1,4-dichlorobenzene.
The peroxo-, hydroperoxo-, superoxo- or alkylperoxo-metal species may be and preferably is generated in situ by adding the desired metal either as pure metal or in the form of a suitable oxide, salt or other derivative. Alternatively, the desired derivative e.g. an acetoacetonate may be formed prior to reaction and added to the reaction mixture.
Suitable metal forms include oxides, anhydrides, acetylacetonates, alkoxymetal derivatives, sulfates, nitrates, halides, oxyhalides, alkylthiocarbamates or metalates with other cations, (e.g. ammonium metavanadate NH
4
VO
3
)
Preferred metals include molybdenum, titanium, vanadium, tungsten, rhenium, selenium, niobium, tantalum and tellurium with vanadium being particularly preferred.
Preferred metal forms include oxides, acetylacetonates, alkoxymetal oxides and oxychlorides.
A discussion of peroxo-, hydroperoxo-, superoxo- and alkylperoxo-metal species can be found in Conte et al. in Organic Peroxides Ed. W. Ando, John Wiley & Sons (1992) (pp 559-598).
Discussion of hydroperoxide oxidising agents and metal derivatives may also be found in U.S. Pat. Nos. 3,350,422; 3,351,635; 3,360,584; 3,360,585; and 3,662,006.
A particular advantage of the present process is that the peroxo-, hydroperoxo-, superoxo- or alkylperoxo-metal species can be and preferably are free of complex ligands.
The metal derivatives can be present in amount equivalent to between 0.001 and 100 mol % of metal. Preferably catalytic amounts of 0.1 to 15 mol % are employed.
When employed as a catalyst the metal derivative may be recycled and regenerated. For example when an oxide such as vanadium pentoxide is used the spent catalyst can be heated in air (cf Polish Patent PL 73-165695; C.A. 87.91418) or treated with hydrogen peroxide.
The acid component of the process according to the invention is selected from formic or an alkanoic acid. Preferred alkanoic acids are lower alkanoic acids containing e.g. 2 to 6 carbon atoms such as acetic, propionic or butyric acid. The preferred acid according to the invention is acetic acid.
The use of solvents may also have a beneficial effect on the process according to the invention. Examples of such solvents include aprotic solvents such as chlorinated solvents e.g. 1,2-dichloromethane, dichloromethane, chloroform, nitrated solvents, e.g. nitromethane; nitrites e.g. acetonitrile, propionitrile, benzonitfile; ketones, e.g. acetone, methylethylketone; alkanes, e.g. hexane; esters e.g. ethylacetate; alcohols e.g. methanol, ethanol, isopropanol; or mixtures thereof.
Reaction temperatures lie between 0 and 150° C. and are preferably in the range of room to elevated (ca 90°) temperature e.g. when employing acetic acid and a vanadium derivative. The reaction is preferably carried out in the substantial absence of water. In certain cases removal of water further increases yield. This is the case for example where the oxidising agent is used in aqueous solution or where the water is generated during the reaction. Removal of water can be achieved for example by carrying out the reaction in the presence of a drying agent such as activated molecular sieves (3 Å or 4 Å), calcium sulphate, magnesium sulphate or acetic anhydride, etc.
In certain cases pH will affect the course of the reaction and therefore the addition of a Lewis acid or a Bronsted acid (cf Kirk Othmer Encyclopedia of Chemical Technology; 4th Edition; Wiley lnterscience) such as p-toluenesulfonic or methanesulfonic acid can increase the yield.
Addition of a salt of the chosen formic or alkanoic acid e.g. dry sodium acetate with acetic acid can increase the yield in certain cases.
The reaction mixture may be mono- or multi- e.g. bi-phasic. Examples of such systems can be found in Bianchi et al. J. Mol. Catal. 83 (1993) 107-116; Bonchio et al. J. Org. Chem. 54 (1989) 4368-4371.
Typically the substrate to be oxidised (1,4-dichlorobenzene) is dissolved in the chosen acid (e.g. acetic acid) and the metal derivative (e.g. a high valency oxide) added followed by the slow addition of the oxidising agent (e.g. aqueous H
2
O
2
). The metal derivative may be deposited on a carrier such as silica, alumina, aluminosilicates, zeolites, coals, titanium oxide, quartz, etc.
The starting material 1,4-dichlorobenzene has the formula
and is a known, commercially available substance.
The desired end product 2,5-dichlorophenol has the formula
and is useful as an intermediate in the preparation of the commercial herbicide dicamba in high isomeric purity (e.g. in substantial absence of 3,5-dichloro-o-anisic acid).
This process involves carboxylation of the 2,5-dichlorophenol to give 2-hydroxy-3,6-dichlorobenzoic acid (a.k.a. 3,6-dichlorosalicylic acid) and methylation of this substrate with subsequent saponification to give high purity dicamba which may be isolated in free acid, salt or ester form (cf e.g. U.S. Pat. No. 3,013,054 for reaction from 2,5-dichlorophenol to dicamba).
The relevant portions of publications and other patent documents cited herein are hereby also incorporated by reference.
The following examples illustrate the invention. Temperatures are in degrees centigrade.


REFERENCES:
patent: 3013054 (1961-12-01), Richter
patent: 4529824 (1985-07-01), Mimoun et al.
patent: 4798837 (1989-01-01), Drabek et al.
patent: 5648562 (1997-07-01), Henrick
patent: 21 01 992 (1972-08-01), None
patent: 0 179 022 (1986-04-01), None
patent: 1 428 271 (1976-03-01), None
patent: 92/18449 (1992-10-01), None
Tetrahedron, vol. 52, No. 11, 1996, pp. 3889-3896, Fujimoto et al.
Journal of Molecul

Affiliated with

Also associated with

Rating

Oxidation process does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Oxidation process, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Oxidation process will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2587535