Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2000-04-27
2001-03-13
Dentz, Bernard (Department: 1625)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
active
06201135
ABSTRACT:
The present invention relates to a process for removing undesirable impurities from 3-(2′-acetoxyethyl)dihydro-2(3H)-furanone of the formula I
3-(2′-acetoxyethyl)dihydro-2(3H)-furanone is a starting material for preparing methyl tetrahydropyran-4-carboxylate, which for its part is an intermediate in the preparation of crop protection agents.
3-(2′-Acetoxyethyl)dihydro-2(3H)-furanone is prepared, for example, by processes that are known per se and described, for example, in U.S. Pat. No. 5,350,863, starting from methyl acetoacetate and ethylene oxide. Another process variant by which 3-(2r-acetoxyethyl)dihydro-2(3H)-furanone is obtainable is described in Dokl. Akad. Nauk SSSR 27 (1940), 956-959 and U.S. Pat. No. 5,283,326.
In both variants, the desired 3-(2′-acetoxyethyl)dihydro-2(3H)-furanone is formed as a mixture with a number of undesirable byproducts, in particular the isomeric dihydro-3-(2-methyl-1,3-dioxolan-2-yl)-2(3H)-furanone II
If I contaminated in this manner is reacted in a continuous gas phase reaction with methanol in the presence of acidic catalysts to give methyl tetrahydropyran-4-carboxylate, considerably lower yields and shorter catalyst onstream times are obtained than when a product of high purity without the byproducts is used. This is probably due to the fact that most byproducts contain sensitive acetal groups which decompose on the surface of the catalyst to oligomeric and polymeric products.
The removal by distillation in particular of II from mixtures comprising I and II can be realized only with difficulties and at high cost, owing to the boiling points, which are very close.
It is an object of the present invention to provide a process by which undesirable byproducts, in particular II, can be removed from mixtures with I without changing I in the process.
We have found that this object is achieved by a process for removing impurities from 3-(2′-acetoxyethyl)dihydro-2(3H)-furanone (I), which comprises initially preparing the 3-(2′-acetoxyethyl)dihydro-2(3H)-furanone containing the undesirable impurities in a manner known per se by acetylating 3-(2′-hydroxyethyl)-dihydro-2-(3H)-furanone, subsequently treating it with strong mineral acids and finally removing the decomposition products of the undesirable impurities from I.
Surprisingly, the desired I is not degraded during treatment with mineral acids and can therefore be obtained in good yield and high purity.
Preferred embodiments of the process according to the invention are disclosed in the subclaims and the description below.
The process according to the invention starts with the mixture of 3-(2′-hydroxyethyl)dihydro-2(3H)-furanone and undesirable impurities which can be obtained by known processes which were described in the introduction.
This mixture is initially acetylated as completely as possible. Preferred acetylating agents are acetic anhydride or acetic acid itself; in principle, however, all acetylating agents known to the person skilled in the art for corresponding acetylations are suitable. The acetylation is generally carried out at temperatures in the range from 40° C. to 200° C., preferably from 60 to 140° C., over a period of from 0.5 to 10, preferably from 0.8 to 5 and in particular from 1 to 3, h.
To ensure complete acetylation, the acetylating agent is generally employed in a molar excess of from 5 to 50%, preferably from 5 to 20%, based on 3-(2′-hydroxyethyl)dihydro-2(3H)-furanone present in the mixture.
In the subsequent step, the acetylation product is treated with strong mineral acids. Preferred mineral acids are hydrochloric acid, nitric acid and, particularly preferably, sulfuric acid. This is employed preferably at at least 80% strength and in particular in the form of concentrated sulfuric acid.
The amount of sulfuric acid used can be varied within wide ranges; in some cases, it was found to be advantageous to use a molar ratio of strong mineral acid, based on the amount of acetylating agent used in the preceding step, in the range of from 1:20 to 1:3, preferably from 1:15 to 1:7 and in particular from 1:8 to 1:12.
For the treatment with the mineral acid, the temperature is generally in the range of from 10 to 80, preferably from 20 to 60 and in particular from 30 to 50° C. The duration of the treatment is generally in the range of from 0.3 to 10, in particular from 1 to 5, h, but can, in principle, be varied within wide limits.
After the treatment with strong mineral acids, the decomposition products of the undesirable impurities, in particular of dihydro-3-(2-methyl-1,3-dioxolan-2-yl)-2(3H)-furanone II, can be removed in a simple manner.
According to a preferred variant, the mineral acid is initially neutralized by addition of base, preferably aqueous alkali metal hydroxide, and the acetic acid formed as coproduct in the acetylation is subsequently, if appropriate, distilled off. Phase separation is subsequently carried out by addition of a suitable organic solvent and water, and the organic phase is then extracted. Suitable organic solvents are in particular aromatic hydrocarbons and especially alkylated benzene derivatives, such as xylene or toluene. The organic extracts are combined and the solvent is removed, and the residue can then be rectified under reduced pressure, giving, in good yield and high purity, the desired product, which may subsequently be processed further. The degree of purity of I can be increased even further by carrying out more than one rectifications in succession. The conditions for the rectification are known per se to the person skilled in the art and described in the literature, so that further details are not required here.
After the process according to the invention has been carried out, the purity of I is generally at least 98, preferably at least 98.5 and particularly preferably at least 99% by weight.
The I obtainable by the process according to the invention can be reacted in a manner known per se in high yield and with good catalyst onstream times to give methyl tetrahydropyran-4-carboxylate. This is an important intermediate in the preparation of crop protection agents.
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patent: 4837346 (1989-06-01), Becker et al.
patent: 5283326 (1994-02-01), Hansen et al.
patent: 5350863 (1994-09-01), Kuekenhoehner et al.
patent: 5371246 (1994-12-01), Borchers et al.
patent: 5466831 (1995-11-01), Schnurr et al.
patent: 246 581 (1987-11-01), None
patent: 584 631 (1994-03-01), None
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Packendorff et al. “Uber Einen Neuen Reaktions—Typus Des Athlyenoxyds (II). Uber Die Bei Der Kondensation Von Malonester Mit Athylenoxyd Entstehenden Nebenprodukte” Dokl. Akad. Nauk SSR 27 (1940) pp. 956-959.
Borchers Dirk
Gotz Norbert
Hartmann Horst
Konig Hartmann
Kükenhöhner Thomas
BASF - Aktiengesellschaft
Dentz Bernard
Keil & Weinkauf
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