Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters
Reexamination Certificate
2000-04-03
2002-09-03
Vollano, Jean F. (Department: 1623)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acid esters
C560S254000, C562S508000
Reexamination Certificate
active
06444843
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to producing of bifunctional compounds having two functional groups, which are highly suitable as a raw material for producing a homo-polyester or co-polyester with ethylene glycols, etc. More specifically, the invention relates to a producing method of (hydroxyalkyl)alicyclic carboxylic acids such as (hydroxyalkyl)cyclohexane carboxylic acids, and also relates to intermediates for producing the same and a producing method of such intermediates.
BACKGROUND OF THE INVENTION
In general, bifunctional compounds having two functional groups have their use as a raw material of various synthetic resins and as various chemical agents such as a solvent, or as a raw material of such chemical agents. Particularly, (hydroxyalkyl)alicyclic carboxylic acids, which are one kind of compounds having an alcoholic hydroxy group and a carboxylic group within the same molecule, and of which (hydroxyalkyl)cyclohexane carboxylic acids in particular, are highly useful as a raw material for producing a homo-polyester or co-polyester with ethylene glycols, etc.
For example, French Patent No. 1,447,136 (Published Date: Jun. 20, 1966) discloses a producing method of 4-hydroxymethylcyclohexane carboxylic acid, which is one type of the (hydroxyalkyl)alicyclic carboxylic acids, in which a benzene ring is hydrogenated under the reaction conditions of the reaction temperature of 200° C. and reaction pressure of 1.47×10
7
Pa, using a p-hydroxymethyl benzoic acid as a reaction substrate and Raney nickel as a catalyst. Also, for example, Japanese Unexamined Patent Publication No. 59188/1997 (Tokukaihei 9-59188) (Published Date: Mar. 4, 1997) discloses a method in which a benzene ring is hydrogenated under the reaction conditions of the reaction temperature of 160° C. and reaction pressure of 4.9×10
6
Pa, using a terephthalic acid as a reaction substrate and tin-modified Raney ruthenium as a catalyst.
However, there has been no established method of inexpensively and industrially producing the p-hydroxymethyl benzoic acid, which is used as a raw material in the method as disclosed in the above French patent 1,447,136, and the above publication does not disclose such a producing method.
(Hydroxymethyl)aromatic carboxylic acids, such as the p-hydroxymethyl benzoic acid as mentioned above are also one type of compounds having an alcoholic hydroxy group and a carboxylic group within the same molecule, and are a bifunctional compound having two functional groups, which makes these compounds highly useful as a raw material for producing a homo-polyester or co-polyester with ethylene glycol, etc.
For example, U.S. Pat. No. 4,130,719 (Published Date: Dec. 19, 1978) discloses a producing method of a p-hydroxymethyl benzoic acid, in which the side chains of terephthalic acid monoester are reduced using sodium borohydride in an amount above a stoichiometric amount (in excess amount). Also, for example, U.S. Pat. No. 4,448,987 (Published Date: May 15, 1984) discloses a method in which terephthalic acid is subjected to hydrogenation using rhenium oxide as a catalyst. Further, Japanese Unexamined Pat. Publication No. 101334/1975 (Tokukaisho 50-101334) (Published Date: Aug. 11, 1975) discloses a method in which a p-toluic acid used as a staring material is irradiated in the presence of halogen (halogenated) to synthesize a p-halomethyl benzoic acid, followed by hydrolysis. Further, Japanese Unexamined Pat. Publication No. 96541/1973 (Tokukaisho 48-96541) (Published Date: Dec. 10, 1973) discloses a method of obtaining a p-hydroxymethyl benzoic acid, which is generated as a by-product in the synthesis of a terephthalic acid by directly oxidating the side chains of p-xylene.
However, the method as disclosed in the above U.S. Pat. No. 4,130,719 requires an excess amount of reducing agent and the p-hydroxymethyl benzoic acid cannot be produced efficiently and inexpensively. Further, the method as disclosed in the U.S. Pat. No. 4,448,987 requires a reduction process using hydrogen, which in turn requires equipment which can withstand the reaction conditions of high temperature and high pressure, and thus this producing method is not suitable for industrial applications. Furthermore, the method as disclosed in Tokuikaisho 50-101334 requires special equipment which can resist corrosion, etc., in the process of halogenation, and thus this producing system is not suitable either for industrial applications. Further, because the method incorporates halogen and halogenated products, it poses the waste and environmental problems. Also, in the method as disclosed in Tokukaisho 48-96541, the p-hydroxymethyl benzoic acid generated as a by-product is obtained, and thus the method suffers from low productively and constancy, and therefore is not suitable for industrial applications.
That is, all of the conventional producing methods as described above are not suitable for industrial applications, and have the problem that the (hydroxymethyl)aromatic carboxylic acids cannot be produced efficiently and inexpensively. Namely, in the method as disclosed in the French Pat. 1,447,136, it is difficult to obtain the p-hydromethyl benzoic acid as a raw material in industrial applications.
Further, the use of nickel or cobalt such as Raney nickel or Raney cobalt as a catalyst for a hydrogenation reaction as disclosed in the above French Pat. 1,447,136 requires a notoriously high partial pressure of hydrogen in the hydrogenation of the benzene ring, and it also requires a reaction at high temperature, thus requiring special equipment which can withstand this reaction conditions. As a result, the target product 4-hydroxymethyl cyclohexane carboxylic acids cannot be produced inexpensively. Meanwhile, with the use of a catalyst containing palladium or platinum for the hydrogenation of the aromatic ring, the reaction conditions can be relatively relieved, but it still has the problem that the hydroxymethyl group is susceptible to hydrogenolysis, and 4-methylcyclohexane carboxylic acid is easily generated as a by-product, and the selectivity of 4-hydroxymethyl cyclohexane carboxylic acid suffers. Further, in the method as disclosed in the above French Pat. 1,447,136, the catalytic activity of the catalyst used is low, and in order to improve the production efficiency, it requires a large amount of catalyst with respect to the p-hydroxymethyl benzoic acid as a reaction substrate.
Thus, for the reasons described above, the producing method as disclosed in the French Pat. 1,447,136 is not suitable for industrial applications.
Meanwhile, with the method as disclosed in Tokukaihei 9-59188, 4-hydroxymethyl cyclohexane carboxylic acid can be obtained under relatively relieved reaction conditions.
However, in the method as disclosed in Tokukaihei 9-59188, in order to obtain the 4-hydroxymethyl cyclohexane carboxylic acid from the terephthalic acid used as a raw material, it requires hydrogenation of the benzene ring and carbonyl group, and stoichiometrically it requires 5 moles of hydrogen for 1 mole of the raw material. That is, the method of Tokukaihei 9-59188 employs a reaction which consumes a large amount of hydrogen. Further, in this reaction, water is generated as a by-product from the terephthalic acid used as a raw material, which makes the basic unit of the raw material larger. For these reasons, with the method of Tokukaihei 9-59188, the 4-hydroxymethyl cyclohexane carboxylic acid cannot be produced inexpensively.
Furthermore, because the product of the reaction, 4-hydroxymethyl cyclohexane carboxylic acid, and the raw material, terephthalic acid, are hardly soluble in the solvent, to obtain the 4-hydroxymethyl cyclohexane carboxylic acid in high purity, special purifying equipment is required.
Further, producing of tin-modified ruthenium to be used as a catalyst would require special equipment for melting a ruthenium metal and aluminium metal at a high temperature to produce Raney alloy. As a result, the cost of producing the catalyst is increased, which in turn increases the cost of produc
Iida Toshiya
Satoh Yuuichi
Tatsumi Jun
Nippon Shokubai Co. , Ltd.
Vollano Jean F.
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