JPH0597769A - Condensed ring-containing compound and its production - Google Patents

Abstract

PURPOSE:To provide a new compound useful as a raw material for polymers having excellent characteristics. CONSTITUTION:A compound of formula I ((n) is 0-2; R1, R2 are H, saturated hydrocarbon; R3 is formyl, hydroxymethyl). For example, 5-hydroxymethylbicyclo [2,2,1]heptane-2,3-dicarboxylic acid. The compound of formula I is obtained by subjecting a compound of formula II, carbon monoxide and hydrogen to a hydroformylation reaction in the coexistence of a noble metal catalyst (e.g. rhodium oxide) and preferably a trisubstituted phosphine or trisubstituted phosphite in a solvent (e.g. methanol) at 60-160 deg.C. Polymers obtained through the compound of formula I have reduced polymerization contraction and have good adhesivity to other raw materials. Good moisture absorbability and dyeability are given to the polymeric compound by the acetalation reaction of the polymeric compound.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a dicarboxylic acid having a norbornane ring having a formyl group or a hydroxymethyl group, a perhydrodimethanonaphthalene ring or a perhydrotrimethanoanthracene ring, and an ester derivative thereof. That is, since the compound of the present invention has one formyl group or hydroxymethyl group and two carboxyl groups or esterified carboxyl groups in a molecule having a bulky alicyclic skeleton, It has a use as a raw material for producing an excellent polymer and a use in which a new property can be imparted to the polymer compound by adding it to the polymer compound.

[0002]

2. Prior Art Journal of Polymer Science Polymer Chemistry Edition Vol. 10 3
191 (1972), bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate, 1,
2,3,4,4a, 5,8,8a-octahydro-1,
4: 5,8-dimethanonaphthalene-2,3-dicarboxylate and 1,2,3,4,4a, 5,8,8a,
9,9a, 10,10a-dodecahydro-1,4: 5,
A process for making 8: 9,10-trimethanoanthracene-2,3-dicarboxylate is described. Also, US Pat. No. 3,413,317 discloses bicyclo [2.2.1] heptane-2,3,5-tricarboxylic acid and ester derivatives thereof.

US Pat. No. 3,413,317 discloses bicyclo [2.2.1] hept-5-ene-2,3.
There is a description of a method for producing a tricarboxylic acid and its ester derivative by reacting a dicarboxylic acid diester or an acid anhydride with carbon monoxide in the presence of an acid catalyst and water or an alcohol, but a formyl group or a hydroxymethyl group. There is no disclosure about a dicarboxylic acid having ## STR4 ## and its ester derivative.

[0004]

An object of the present invention is to provide a compound useful as a raw material for producing a polymer having excellent properties.

[0005]

According to the present invention, the following inventions are provided. The following general formula (I)

[0006]

[Chemical 6]

(In the formula, n represents 0, 1 or 2, and R ₁
And R ₂ each represents a hydrogen atom or a saturated hydrocarbon group, and R ₃ represents a formyl group or a hydroxymethyl group).

The following general formula (II)

[0009]

[Chemical 7]

The compound represented by the formula (wherein n, R ₁ and R ₂ are as defined above) is reacted with carbon monoxide and hydrogen.
1)

[0011]

[Chemical 8]

A process for producing a fused ring-containing compound represented by the formula (wherein n, R ₁ and R ₂ have the same meanings as described above).

General formula (I-1)

[0014]

[Chemical 9]

A compound represented by the following formula (wherein n, R ₁ and R ₂ have the same meanings as described above) is subjected to a reduction reaction.

[0016]

[Chemical 10]

(Wherein n is 0, 1 or 2 and R ₁ and R ₂ are each a hydrogen atom or a saturated hydrocarbon group).

With respect to the general formula relating to the present invention, the number of carbon atoms of the saturated hydrocarbon group represented by R ₁ and R ₂ is usually 1 to
It is preferably in the range of 8 and more preferably in the range of 1 to 6. As the saturated hydrocarbon group, for example, an alkyl group (eg, methyl group, ethyl group, propyl group,
Isopropyl group, butyl group, pentyl group, hexyl group,
C1-C8 alkyl group such as octyl group, preferably C1-C6 alkyl group, cycloalkyl group (for example, cyclopropyl group, cyclopentyl group, cyclohexyl group etc. C3
~ 6 cycloalkyl groups) and the like.

Among the compounds represented by the general formula (I) of the present invention, the condensed ring-containing compound represented by the general formula (I-1) in which R ₃ is a formyl group is represented by the following general formula (II).

[0020]

[Chemical 11]

(In the formula, n represents 0, 1 or 2, and R ₁
And R ₂ each represent a hydrogen atom or a saturated hydrocarbon group), which is produced by a so-called hydroformylation reaction in which carbon monoxide and hydrogen are reacted.

The general formula (II) used in the present invention
In the compound represented by the formula ( ₁ ), a compound in which R ₁ and R ₂ are saturated hydrocarbon groups can be produced from fumaric acid diester or maleic acid diester and cyclopentadiene by utilizing a known Diels-Alder reaction. it can.

In the compound represented by the general formula (II), the compound in which R ₁ and R ₂ are hydrogen atoms is produced by hydrolyzing the above compound in which R ₁ and R ₂ are saturated hydrocarbon groups. can do. It can also be produced by hydrolyzing a compound obtained by a known Diels-Alder reaction from maleic anhydride and cyclopentadiene.

In the above hydroformylation reaction,
Known noble metal catalysts such as cobalt-based catalysts, rhodium-based catalysts, and platinum-based catalysts can be used. Among them, rhodium-based catalysts are preferable because they have high catalytic activity and few side reactions.
The rhodium-based catalyst is a rhodium carbonyl complex compound,
Alternatively, any rhodium compound capable of forming a rhodium carbonyl complex compound in the reaction system, or a catalyst in which rhodium metal is supported on a suitable carrier such as activated carbon can be used. Many such rhodium-based catalysts are known, but rhodium oxide, rhodium acetylacetonate, rhodium chloride, organic carboxylate rhodium, Rh ₄ (CO)
₁₂ , Rh ₆ (CO) ₁₆ , RhCl (PPh ₃ ) ₃ [wherein PPh ₃ represents triphenylphosphine],
[RhCl (CO) ₂ ] ₂ , HRh (CO) (PPh ₃ )
₃ , Rh (CO) ₂ (AcAc) [in the formula, AcAc represents an acetylacetonate group] and the like can be mentioned as suitable specific examples thereof.

The catalyst is preferably 0.001 to 10 milligram atom / catalyst metal atom in the reaction mixture.
It is used at a concentration of 1 liter, more preferably 0.01 to 5 mg atom / liter.

When a rhodium-based catalyst is used, it is necessary to allow an excessive amount of trisubstituted phosphine or trisubstituted phosphite to coexist with the catalyst so that side reactions such as hydrogenation reaction are suppressed and the hydroformylation reaction is selected. Is preferable, the thermal stability of the rhodium catalyst is increased, and the catalytic activity life is extended.

Specific examples of the tri-substituted phosphine which can be used include tributylphosphine, trialkylphosphine such as tri (2-ethylhexyl) phosphine,
And triarylphosphines such as triphenylphosphine, tritolylphosphine and tris (2-methylphenyl) phosphine. Specific examples of the tri-substituted phosphite include triphenyl phosphite, tris (2-methylphenyl) phosphite, tris (2-t-butylphenyl) phosphite, tris (2,4-dit-butylphenyl) phosphite. Examples include triaryl phosphite such as phyt.

The amount of the tri-substituted phosphine or tri-substituted phosphite used is preferably 5 to 500 equivalents, and more preferably 1 equivalent to 1 gram atom of rhodium.
It is within the range of 0 to 300 equivalents.

The hydroformylation reaction can be carried out in the absence of a solvent, but it can also be carried out in the presence of a suitable organic solvent inert to the reaction. In particular, when using a rhodium-based catalyst and trisubstituted phosphine or trisubstituted phosphite, it is desirable to carry out the reaction in the coexistence of an organic solvent that dissolves these. Specific examples of such a solvent include alcohols such as ethanol and butanol; saturated aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; benzene, toluene, xylene,
Examples thereof include aromatic hydrocarbons such as alkylnaphthalene; and ethers such as tetrahydrofuran.

The temperature of the hydroformylation reaction is 60 to 1
It is preferably carried out at a temperature in the range of 60 ° C.,
More preferably, it is carried out at a temperature within the range of 130 ° C.
When the reaction temperature is lower than 60 ° C, the reaction rate is low,
If it exceeds 160 ° C, it may be difficult to maintain the stability of the noble metal catalyst.

The reaction pressure depends on the reaction temperature used, but in practice, it is usually about 10 to 300 atm, preferably 2 atm.
It is selected from the range of 0 to 200 atm. Although it is possible to carry out the reaction under a pressure higher than 300 atm, 300 atm or less is industrially advantageous from the viewpoint of equipment and operation.

The hydrogen / carbon monoxide ratio used in the reaction is preferably in the range of about 5/1 to 1/5 as the hydrogen / carbon monoxide molar ratio of the gas entering the reactor.
It should be noted that a gas inert to the hydroformylation reaction, such as methane, ethane, propane, nitrogen, helium, argon, carbon dioxide gas, etc., may coexist in the reaction system.

The time required for the hydroformylation reaction is the reaction conditions such as the reaction temperature to be employed, the catalyst concentration, the concentration of the compound represented by the general formula (II) as the starting compound, the reaction pressure and the form of the reactor used. It usually changes by 10
Within the range of minutes to 50 hours.

After completion of the hydroformylation reaction, the product represented by the general formula (I-1) is separated from the reaction mixture by a conventional isolation operation. General formula (I
In -1), the compound in which n is 0 or 1 can be isolated by a usual distillation operation. However, the compound in which n is ₂ is represented by R ₁ and R ₂ even if n is 1. A compound having a saturated carbon group with a large number of carbon atoms has a high boiling point, and thus it may be difficult to isolate it by an ordinary distillation operation. In such a case, it is desirable to use means such as recrystallization or extraction.

The compound represented by the general formula (I-2) can be produced by subjecting the compound represented by the general formula (I-1) to a reduction reaction. This reduction reaction can be carried out on a hydroformylation reaction mixture containing a compound represented by the general formula (I-1), and can be represented by the general formula (I-1) isolated from the reaction mixture. It is also possible to carry out on the compounds mentioned. The reduction reaction can be carried out by reduction with a reagent such as sodium borohydride, but industrially it is advantageous to reduce with hydrogen gas in the presence of a catalyst.

In the reduction reaction with hydrogen gas, any known catalyst used for the reduction of the formyl group can be used. As a preferred specific example, Raney nickel, Raney cobalt, nickel diatomaceous earth, copper chromium oxide,
Examples thereof include palladium and platinum oxide supported on activated carbon.

The catalyst is preferably used in a concentration within the range of about 0.001 to 10% by weight based on the reaction mixture.

The reduction reaction is usually carried out at a temperature within the range of 30 to 250 ° C., although it depends on the type of catalyst used. When the reaction temperature is less than 30 ° C, the reaction rate is usually low, and when it exceeds 250 ° C, it may be difficult to maintain the stability of the catalyst.

The pressure of the reduction reaction may vary depending on the reaction temperature and the catalyst used, but in practice, it is usually about 1 to 3.
It is selected from the range of 00 atm. Although it is possible to carry out the reaction under a pressure higher than 300 atm, 300 atm or less is industrially advantageous from the viewpoint of equipment and operation. It should be noted that even if a gas inert to the reduction reaction with hydrogen gas, such as methane, ethane, propane, nitrogen, helium, argon, carbon dioxide, etc. coexists in the reaction system, it does not matter.

The time required for the reduction reaction varies depending on the reaction temperature employed, the catalyst concentration, the concentration of the starting compounds, the reaction pressure, the form of the reactor used, etc., but it is usually 10 minutes to 5 minutes.
It is within the range of 0 hours.

The reduction reaction can be carried out in the absence of a solvent, but can also be carried out in the presence of a suitable solvent inert to the reaction. Specific examples of such a solvent include water;
Alcohols and hydrous alcohols such as ethanol and butanol; esters such as methyl acetate and ethyl acetate; saturated aliphatic hydrocarbons such as pentane, hexane, heptane, octane; aromatic hydrocarbons such as benzene, toluene, xylene, alkylnaphthalene; and Ethers such as tetrahydrofuran can be mentioned.

After the reduction reaction is completed, the product is isolated by a known method such as distillation, recrystallization and extraction.

The hydroformylation reaction and reduction reaction can be carried out in either a stirred reaction tank or a tower reaction tank.

[0044]

The compound represented by the general formula (I) of the present invention is one formyl group or hydroxymethyl group and two carboxyl groups or esterified carboxyl groups in a molecule having a bulky alicyclic skeleton. And is a useful compound that can be induced into various compounds. For example, a compound obtained by reacting a compound having a hydroxymethyl group with acrylic acid to form an acrylate, and a polymer obtained by radically polymerizing this acrylate has a bulky alicyclic skeleton having a carboxyl group or an esterified carboxyl group. Since it is a molecule, it has good adhesiveness to other materials in addition to the feature of low polymerization shrinkage. Further, it is also possible to add the compound of the present invention to a polymer compound having a hydroxyl group by acetalization reaction of the formyl group, and to add good hygroscopicity and dyeability to the polymer compound.

Further, the compound represented by the general formula (I) is subjected to a known oxidation reaction to convert the formyl group or the hydroxymethyl group into a carboxyl group to obtain the corresponding tricarboxylic acid and its ester derivative. You can

[0046]

EXAMPLES The present invention will be described in detail below with reference to examples. Example 1 A magnetic stir autoclave made of SUS316 having a content of 1 liter was charged with bicyclo [2.2.1] hept-5-ene-.
2,3-dicarboxylic acid dimethyl ester 250 g, toluene 250 ml, HRh (CO) (PPh ₃ ) ₃ 1.0
g and PPh ₃ 6.6 g were charged, and the inside of the system was sufficiently replaced with a mixed gas having a carbon monoxide / hydrogen molar ratio of 1/1, and then the pressure in the system was maintained at 90 atm with stirring. It was heated and the temperature in the system was raised to 130 ° C. in 30 minutes. Stirring was continued for another 5 hours while maintaining the internal temperature at 130 ° C. During the reaction, the pressure of the autoclave is always maintained at 90 atm, a mixed gas with a carbon monoxide and hydrogen molar ratio of 1/1 is continuously supplied through a pressure control valve, and the gas flow rate from the autoclave is about It was adjusted to be 5 liters / hour.

After completion of the reaction, the reaction mixture was taken out of the autoclave, toluene was distilled off, and the residue was subjected to vacuum distillation to obtain 180 g of a fraction having a boiling point of 112 to 116 ° C. at 0.3 mmHg.

As a result of ¹ H-NMR analysis, the main fraction was 5-formylbicyclo [2.2.1] heptane-2,3.
-Dicarboxylic acid dimethyl ester was confirmed.

Example 2 The autoclave used in Example 1 was charged with the 5-formylbicyclo [2.2.1] heptane-2,3 obtained in Example 1.
Charging 100 g of dicarboxylic acid dimethyl ester, 350 g of ethyl acetate and 10 g of Raney nickel catalyst,
After the system was sufficiently replaced with hydrogen gas, the system was heated under stirring while maintaining the system pressure at 50 atm, and the system temperature was raised to 80 ° C. in 20 minutes. While maintaining the internal temperature at 80 ° C., stirring was continued for another 5 hours. During the reaction, hydrogen gas was continuously supplied through a pressure control valve so that the pressure of the autoclave was always maintained at 50 atm.

After completion of the reaction, the reaction mixture was taken out from the autoclave, the Raney nickel catalyst was filtered, ethyl acetate was distilled off, and then the residue was subjected to vacuum distillation to give 0.1 to 0.1.
73 g of a fraction having a boiling point of 120 to 130 ° C. at 0.2 mmHg
Obtained.

As a result of ¹ H-NMR analysis, it was confirmed that the main fraction was 5-hydroxymethylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid dimethyl ester.

Example 3 The 5-hydroxymethylbicyclo [2.2.1] obtained in Example 2 was placed in a glass container having a content of 300 ml equipped with a stirrer.
Heptane-2,3-dicarboxylic acid dimethyl ester 5
0 g, 100 g of water, 400 g of methanol and 20 g of sodium hydroxide were charged, and the mixture was stirred at 80 ° C. for 2 hours.

After the reaction was completed, the reaction mixture was acidified with hydrochloric acid to precipitate the product, which was washed with water to obtain the product.

As a result of analysis by ¹ H-NMR, the obtained product was 5-hydroxymethylbicyclo [2.2.1].
It was confirmed to be heptane-2,3-dicarboxylic acid.

Example 4 In the autoclave used in Example 1, 1, 2, 3,
4,4a, 5,8,8a-octahydro-1,4: 5,
200 g of 8-dimethanonaphthalene-2,3-dicarboxylic acid dimethyl ester, 300 ml of toluene, Rh (CO)
₂ (AcAc) 0.4 g and tris (2,4-di-t-
(Butylphenyl) phosphite (12 g) was charged, the system was sufficiently replaced with a mixed gas having a carbon monoxide / hydrogen molar ratio of 1/1, and then the system pressure was maintained at 90 atm.
The mixture was heated with stirring, and the temperature in the system was raised to 130 ° C. in 30 minutes. Stirring was continued for another 5 hours while maintaining the internal temperature at 130 ° C. During the reaction, the pressure of the autoclave is always maintained at 90 atm, a mixed gas with a carbon monoxide and hydrogen molar ratio of 1/1 is continuously supplied through a pressure control valve, and the gas flow rate from the autoclave is about It was adjusted to be 5 liters / hour.

After the reaction was completed, the reaction mixture was taken out of the autoclave, toluene was distilled off, and the residue was subjected to vacuum distillation to obtain 125 g of a fraction having a boiling point of 160 to 170 ° C. at 0.3 mmHg.

As a result of ¹ H-NMR analysis, it was confirmed that this fraction was 6-formyldecahydro-1,4: 5,8-dimethanonaphthalene-2,3-dicarboxylic acid dimethyl ester.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C07C 67/313 69/757 Z 9279-4H

Claims (3)

[Claims] 1. The following general formula (I): (Wherein n represents 0, 1 or 2, R ₁ and R ₂ each represent a hydrogen atom or a saturated hydrocarbon group, and R ₃ represents a formyl group or a hydroxymethyl group). Compound. 2. The following general formula (II): (Wherein n represents 0, 1 or 2 and R ₁ and R ₂ represent a hydrogen atom or a saturated hydrocarbon group, respectively) and carbon monoxide and hydrogen are reacted. The following general formula (I-1): (In the formula, n, R ₁ and R ₂ are as defined above). 3. A compound represented by the general formula (I-1): (Wherein n represents 0, 1 or 2 and R ₁ and R ₂ each represent a hydrogen atom or a saturated hydrocarbon group), and the compound is subjected to a reduction reaction. (I-2) (In the formula, n, R ₁ and R ₂ are as defined above).