Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acids and salts thereof
Patent
1997-03-27
1998-01-20
Shippen, Michael L.
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acids and salts thereof
560204, 562521, C07C 5110
Patent
active
057103232
DESCRIPTION:
BRIEF SUMMARY
TECHNICAL FIELD
The present invention relates to processes for producing monocarboxylic acids and/or dicarboxylic acids, particularly, to processes for producing a good yield of monocarboxylic acids and/or dicarboxylic acids by the reaction of compounds selected from saturated hydrocarbons, saturated monocarboxylic acids and saturated monocarboxylic esters with carbon monoxide and water.
BACKGROUND ART
Production of carboxylic acids by the reaction of alcohols or olefins with carbon monoxide in strong acids, such as sulfuric acid, followed by hydrolysis with water is called the Koch's reaction or the Koch-Harf reaction and has been widely applied for a long time. In a recent application (variation) of the Koch's reaction, saturated hydrocarbons are used as starting materials instead of alcohols or olefins to obtain useful carboxylic acids or mixtures thereof from various saturated hydrocarbons or petroleum distillates of lower value. Strictly speaking, the reaction of saturated hydrocarbons with carbon monoxide and water to produce carboxylic acids is not the so-called Koch's reaction, but is often called the Koch's reaction of saturated hydrocarbons (the Koch's reaction in a broader sense) because of the similarity in reaction.
The marked difference between the so-called Koch's reaction using as starting materials alcohols or olefins and the Koch's reaction in a broader sense is the difference in the reactivity of the starting materials.
The former Koch's reaction is rarely restricted in starting materials and catalysts, since alcohols and olefins of 3 or more carbon atoms, whether normally linear, branched or cyclic, are so reactive as to easily form alkyl cations, and various strong acid catalysts are effective as catalysts. Industrially common catalysts are of sulfuric acid systems because of their high activity and low cost. The use of sulfuric acid, however, gives product carboxylic acids contaminated with sulfur and tends to cause emission of an offensive odor. Therefore, development of new catalysts has been an important problem for the prevention or reduction of such an offensive odor rather than for the improvement of activity. For example, in Japan Patent Application Unexamined Publication No. 62-164645 are proposed catalysts comprising sulfuric acid and phosphoric acid as catalysts which reduce the offensive odor due to the contamination of the product carboxylic acids with sulfur. As an example of the Koch's reaction of alcohols or olefins using catalysts containing no sulfuric acid, a reaction using as a catalyst trifluoromethane-sulfonic acid, which is an organic super acid, is proposed (J. C. S. Parkin I, 1979, p2441).
To the contrary, the Koch's reaction of saturated hydrocarbons is severely restricted in reaction materials since the reactivity of saturated hydrocarbons is low and varies widely depending on structures, and the catalysts therefor also involve many technical problems to be solved.
For example, it is known to produce carboxylic acid by the Koch's reaction of saturated hydrocarbons with carbon monoxide in the coexistence of catalysts comprising sulfuric acid and metal compounds with olefins or alcohols as agents generating alkyl cations (Japan Patent Application Examined Publication Nos. 52-8285 and 52-8286). The method, however, has the considerable defect that the catalysts of low acidity cause the synthesis of carboxylic acids from saturated hydrocarbons containing tertiary hydrogen atoms, but hardly from saturated hydrocarbons containing no tertiary hydrogen atoms.
It is also reported that carboxylic acids can be synthesized even from saturated hydrocarbons containing no tertiary hydrogen atoms by using super acid catalysts, which are called "Magic Acids" and are mixtures of strong acids and Lewis acids such as HF-SbF.sub.5 (Chem. Lett., 1983, p17). These catalysts, however, are extremely corrosive and inapplicable to industrial uses.
The above-described trifluoromethane-sulfonic acid (CF.sub.3 SO.sub.3 H) is a super acid, but generally cannot cause synthesis of carbox
REFERENCES:
patent: 3965132 (1976-06-01), Norell
patent: 5034398 (1991-07-01), Drent
Booth, J. C. S. Perkin I, pp. 2441-2446, 1979.
Farooq, J Am. Chem. Soc., vol. 110, pp. 864-867, 1988.
Kato Tadashi
Okada Yoshio
Okuda Ryoichi
Idemitsu Petrochemical Co. Ltd.
Shippen Michael L.
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