Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
2000-09-26
2002-06-25
Shippen, Michael L. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C568S446000
Reexamination Certificate
active
06410809
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a 1,1-cyclohexanedimethanol compound and a process for producing productive intermediates therefor. More particularly, the present invention relates to a process of producing a 1,1-cyclohexanedimethanol compound having a substituent group at least at the 2-position thereof, useful as a raw material for polyesters, unsaturated polyesters, alkyds, polyurethanes, epoxy resins, acrylic resins, etc., or as a raw material for functional organic compounds, to a process of producing a 3-cyclohexene-1-carbaldehyde compound having a substituent group at least at the 6-position thereof, which is a productive intermediate for the 1,1-cyclohexanedimethanol compound, to a process of producing a 1-hydroxymethyl-3-cyclohexene-1-carbaldehyde compound having a substituent group at least at the 6-position thereof, and to novel 1-hydroxymethyl-6-methyl-3-cyclohexene-1-carbaldehyde.
BACKGROUND ART
1,1-cyclohexanedimethanol compounds having a substituent group at the 2-position thereof are compounds useful as a raw material for resins. JP-A-11-35665 discloses a polyester having high heat resistance, transparency and resistance to hydrolysis derived from a 1,1-cyclohexanedimethanol compound having a substituent group at the 2-position thereof as a starting material. Also, JP-A-11-80305 and JP-A-11-189637 disclose polyurethanes having increased heat resistance derived from the above compound as a starting material of the polyurethane.
As the process of producing the 1,1-cyclohexanedimethanol compound having a substituent group at the 2-position thereof, there is a report by Shortridge, et al. on, for example, 2-methyl-1,1-cyclohexanedimethanol (R. W. Shortridge, et al., J. Am. Chem. Soc., 70, 946 (1948)). According to this process, 6-methyl-3-cyclohexene-1-carbaldehyde obtained by thermal Diels-Alder reaction between butadiene and crotonaldehyde is subjected to Cannizzaro reaction with formaldehyde in the presence of an alkali to synthesize 6-methyl-3-cyclohexene-1,1-dimethanol, followed by hydrogenating the double bond thereof to produce 2-methyl-1,1-cyclohexanedimethanol. However, this process has the problems that the thermal Diels-Alder reaction is low in yield, that the reaction has the danger of runaway or the like so that it is difficult to control it, and that formic acid salts, etc. by-produced in the Cannizzaro reaction in the second stage will deteriorate the quality of product so that a high load is imposed on the system for the separation and purification in order to remove the byproducts. Generation of byproducts will lead to an increase in the units of alkali and formaldehyde and therefore, the process is unsatisfactory for industrial application.
The Diels-Alder reaction between a &bgr;-substituted-&agr;,&bgr;-unsaturated aldehyde and a chain conjugated diene compound requires that the reaction be carried out at a high temperature above 100° C. in order to increase the reaction rate since the reaction site of the &bgr;-substituted-&agr;,&bgr;-unsaturated aldehyde is an internal double bond so that the reactivity is very low. However, under high temperature conditions, a side reaction such as polymerization of the chain conjugated diene compound occurs and therefore it is difficult to practice the reaction in high yields. The rapid increase in reaction rate due to heat generation makes it impossible to control the reaction so that there is a high risk that the runaway of reaction, explosion, etc. will be caused. Therefore, use is made of a catalyst which enables the reaction to be practiced efficiently and at low temperatures.
As for the catalyst for the Diels-Alder reaction between a &bgr;-substituted-&agr;,&bgr;-unsaturated aldehyde and a chain conjugated diene compound, examples of using aluminum chloride or alkylaluminum halide have been reported. The yields are at most about 50%, which are industrially unsatisfactory (Bull. Chem. Soc., 45, 1553 (1972)).
Furthermore, the examples of using boron trifluoride compounds have been reported (J. Org. Chem. USSR, 7, 2459 (1971), Russian J. Org. Chem., 11, 978 (1975), Russian J. Org. Chem., 21, 1320 (1985)). The replicated experiments of the reaction using boron trifluoride ether complex as a catalyst conducted by the present inventors proved that the reaction of a &bgr;-substituted-&agr;,&bgr;-unsaturated aldehyde up to a high conversion resulted in an increase in high boiling matters and a considerable decrease in selectivity of the reaction.
The above literature (J. Org. Chem. USSR, 7, 2459 (1971)) shows an example of the reaction between isoprene and crotonaldehyde using a tin (IV) chloride pentahydrate catalyst. This process has the disadvantage in that the reaction rate is low and the catalyst gradually undergoes hydrolysis with the moisture in the catalyst to form hydroxide or oxide of tin, thus causing deactivation or insolubilization of the catalyst.
As stated above, there has been known no technology that enables the Diels-Alder reaction between a &bgr;-substituted-&agr;,&bgr;-unsaturated aldehyde and a chain conjugated diene compound to proceed in high yields.
Next, as the process of producing a 1,1-cyclohexanedimethanol compound having a substituent group at the 2-position thereof from a 3-cyclohexene-1-carbaldehyde having a substituent group at the 6-position thereof obtained by the Diels-Alder reaction, there is known a process which includes the above-described Cannizzaro reaction between a 3-cyclohexene-1-carbaldehyde having a substituent group at the 6-position thereof and formaldehyde and addition of hydrogen to double bond subsequent thereto. No other production route has been known on a 1,1-cyclohexanedimethanol compound having a substituent group on the 2-position thereof.
As for the production method for a 1,1-cyclohexanedimethanol compound having no substituent group on the 2-position thereof, JP-A-53-65808 (U.S. Pat. No. 4,181,810) discloses a process in which 1-hydroxymethyl-3-cyclohexene-1-carbaldehyde is prepared by the aldol reaction between 3-cyclohexene-1-carbaldehyde and formaldehyde and then reduced. By practicing the aldol reaction between 3-cyclohexene-1-carbaldehyde and formaldehyde using a cation exchange resin as a catalyst according to this process and hydrogenating the aldehyde group of the product using an Ni—Cr—Al catalyst, the carbon-carbon double bond is hydrogenated accessorily to obtain cyclohexane-1,1-dimethanol. However, the yield of cyclohexane-1,1-dimethanol is about 80% of the starting material of the reaction and still unsatisfactory industrially.
Furthermore, the reaction for obtaining 2-substituted-1,3-propanediol by the aldol reaction of an aliphatic aldehyde - hydrogenation reaction is well known for the production process of neopentyl glycol, for example. For example, JP-B-49-11684 discloses a method in which the reaction between isobutyl aldehyde and formaldehyde is carried out using an alkali hydroxide catalyst and then the aldehyde group of the product is hydrogenated using a Cu—Cr catalyst to obtain neopentyl glycol.
DISCLOSURE OF THE INVENTION
1) Object of the Invention
The prior art in which a &bgr;-substituted-&agr;,&bgr;-unsaturated aldehyde and a chain conjugated diene are used as starting materials to produce a 1,1-cyclohenxanedimethanol having a substituent group at the 2-position thereof in multiple steps has problems in that reaction yield in each step is low, byproducts are generated, and so on and no processes have been known that are satisfactory industrially.
Therefore, an object of the present invention is to provide a process of efficiently producing a 1,1-cyclohexanedimethanol compound having a substituent group at the 2-position thereof, industrially useful as a raw material for polyesters, unsaturated polyesters, alkyds, polyurethanes, epoxy resins, acrylic resins, etc., or as a raw material for functional organic compounds.
Further, another object of the present invention is to provide a process of producing a 3-cyclohexene-1-carbaldehyde compound having a substituent group at the 6-position thereof, which is a pr
Honda Yoshihiro
Kaneda Masato
Showa Denko K.K.
Sughrue & Mion, PLLC
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