JP2990275B1 - Mercury-catalyzed synthesis of tertiary carboxylic acids - Google Patents

Abstract

Kind Code: A1 The present invention provides a method for selectively synthesizing a tertiary carboxylic acid or an ester thereof under mild conditions. In a strong acid, at least one compound selected from the group consisting of olefins and alcohols comprises:
A method for synthesizing a tertiary carboxylic acid or an ester thereof by reacting carbon monoxide and then adding water or an alcohol, wherein the reaction is carried out in the presence of a mercury catalyst. A method for synthesizing the ester.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for synthesizing a tertiary carboxylic acid or an ester thereof.

[0002]

BACKGROUND OF THE INVENTION Tertiary carboxylic acids are generally synthesized by the reaction of high pressure carbon monoxide with olefins in strong acids. However, in such a synthesis method, since the reaction conditions are high temperature and high pressure, polymerization of the raw materials cannot be avoided, dimer or trimer carboxylic acid is by-produced, and secondary carboxylic acid is also produced. By-produce. Therefore, in such a method, the selectivity of the tertiary carboxylic acid is not high.

[0003] Derivatives of tertiary carboxylic acids are hardly hydrolyzed because they have two alkyl groups at the α-position of the carboxyl group, and are high-grade paints, high-grade surfactants, etc. having acid resistance, heat resistance and weather resistance. It is attracting attention. But,
If the secondary carboxylic acid is slightly mixed, the acid resistance, heat resistance and weather resistance of the product are drastically reduced because the hydrolysis resistance of the secondary carboxylic acid is lower by one digit.

[0004]

Accordingly, an object of the present invention is to provide a method for selectively synthesizing a tertiary carboxylic acid or its ester under mild conditions.

[0005]

Means for Solving the Problems The present inventor has conducted various studies to find a new method which can solve or reduce the problems of the prior art as described above. Or, a method for selectively synthesizing the ester has been intensively studied. As a result, they have found that the above object can be achieved by using a mercury catalyst, and have completed the present invention. That is, the present invention relates to a method for synthesizing the following tertiary carboxylic acid or an ester thereof: In a method of synthesizing a tertiary carboxylic acid by reacting carbon monoxide with at least one compound selected from the group consisting of olefins and alcohols in a strong acid and then adding water, the reaction is carried out using a mercury catalyst. A method for synthesizing a tertiary carboxylic acid, which is carried out in the presence.

[0006] 2. In a method of synthesizing a tertiary carboxylic acid ester by reacting carbon monoxide with at least one compound selected from the group consisting of olefins and alcohols in a strong acid, and then adding an alcohol, the reaction is carried out using a mercury catalyst. A method for synthesizing a tertiary carboxylic acid ester, which is carried out in the presence of

[0007] 3. In a strong acid, a carbon monoxide is reacted with at least one compound selected from the group consisting of a diene, a diol and a compound having at least one double bond and at least one hydroxyl group, and then tertiary is obtained by adding water. A method for synthesizing a dicarboxylic acid, wherein the reaction is performed in the presence of a mercury catalyst.

[0008] 4. In a strong acid, a carbon monoxide is reacted with at least one compound selected from the group consisting of a diene, a diol, and a compound having at least one double bond and one hydroxyl group, followed by adding an alcohol to form a third compound. A method for synthesizing a tertiary dicarboxylic acid ester, wherein the reaction is carried out in the presence of a mercury catalyst.

[0009] 5. In a method of synthesizing a tertiary carboxylic acid by reacting carbon monoxide with at least one saturated hydrocarbon compound in the presence of an alcohol or an olefin in a strong acid, and then adding water, the reaction is carried out using a mercury catalyst. A method for synthesizing a tertiary carboxylic acid, which is carried out in the presence of:

[0010] 6. In a method of synthesizing a tertiary carboxylic acid ester by reacting carbon monoxide with at least one saturated hydrocarbon compound in the presence of an alcohol or an olefin in a strong acid, and then adding the alcohol, A method for synthesizing a tertiary carboxylic acid ester, which is carried out in the presence of a catalyst.

7. At least one selected from the group consisting of sulfuric acid, sulfuric acid-phosphoric acid, hydrofluoric acid, FSO ₃ H, boron trifluoride, and trifluoromethanesulfonic acid;
7. The method according to any one of the above 1 to 6, wherein the method is a seed.

8. In a method of synthesizing a tertiary carboxylic acid by reacting carbon monoxide with at least one saturated hydrocarbon compound in a super strong acid, and then adding water, the reaction is performed in the presence of a mercury catalyst. A method for synthesizing a tertiary carboxylic acid, the method comprising:

9. Super strong acid is sulfuric acid-sulfur trioxide, ClS
O ₃ H, 100% FSO ₃ H, FSO ₃ H—SO ₃ , FSO
9. The synthesis method according to the above item 8, wherein the synthesis method is at least one selected from the group consisting of ₃ H-SbF ₅ and HF-SbF ₅ .

10. The mercury catalyst is mercury sulfate (I, II),
Mercury acetate (I, II), mercury fluoride (I), mercury oxide (I
The method according to any one of the above items 1 to 9, wherein the method is at least one selected from the group consisting of I), mercury hydroxide (II) and mercury sulfide (II).

11. The mercury catalyst is (a) mercury and (b) SO
₃ and synthesis method described in any one of the above 1 to 9, wherein the at least one selected from the group consisting of S ₂ O ₆ F _2.

12. The mercury catalyst was previously dissolved in a strong acid or a super strong acid, and (a) mercury sulfate (I, II), mercury acetate (I, I
Prepared from at least one mercury compound selected from the group consisting of I), mercury fluoride (I), mercury oxide (II), mercury hydroxide (II), and mercury (II) sulfide; and (b) carbon monoxide. 10. The synthesis method according to any one of 1 to 9 above, wherein

13. Preparing a mercury catalyst from at least one selected from the group consisting of (a) mercury, (b) carbon monoxide, and (c) SO ₃ and S ₂ O ₆ F _{2 in} a strong acid or super strong acid in advance. 10. The synthesis method according to any one of the above 1 to 9, wherein

[0018]

DETAILED DESCRIPTION OF THE INVENTION According to the present invention, a tertiary carboxylic acid is produced by reacting carbon monoxide with at least one compound selected from the group consisting of olefins and alcohols in a strong acid and then adding water. The method for synthesizing an acid includes a method for synthesizing a tertiary carboxylic acid, wherein the reaction is performed in the presence of a mercury catalyst.

Further, the present invention provides a tertiary carboxylic acid ester by reacting carbon monoxide with at least one compound selected from the group consisting of olefins and alcohols in a strong acid, and then adding an alcohol. And a method for synthesizing a tertiary carboxylic acid ester, wherein the reaction is carried out in the presence of a mercury catalyst.

The mercury catalyst used in the present invention is at least one selected from the group consisting of mercury and mercury compounds having a ligand having a low coordination force to monovalent or divalent mercury ions. Such mercury compounds include, for example, mercury sulfate (I, II), mercury acetate (I, II), mercury fluoride (I), mercury oxide (II), mercury hydroxide (II), mercury sulfide (II) ) And the like. As the mercury catalyst of the present invention, at least one selected from the group consisting of mercury and mercury compounds can be used.

The catalytically active species in the reaction of the present invention is represented by Formula 1
([Hg (CO) _n ] ^{a +} , n = 1,2; a = 1,2) (Equation 1).

[0022]

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Accordingly, in the mercury catalyst of the present invention, at least one selected from the group consisting of mercury catalysts may be added to the reaction system as it is.
(a) at least one selected from the group consisting of mercury catalysts;
(b) A reaction product of carbon monoxide may be used. As the mercury catalyst, the latter is preferable because of its higher catalytic activity.

When mercury is used as a mercury catalyst,
An oxidizing agent is allowed to coexist. This oxidizing agent oxidizes mercury, and is not particularly limited as long as it has an oxidizing power capable of oxidizing mercury in a strong acid or a super strong acid.
Specific examples include SO ₃ (sulfur trioxide), S ₂ O ₆ F _{2 and the} like, and preferably SO ₃ . When using mercury as a mercury catalyst, mercury and an oxidizing agent may be added to the reaction system as they are, but in a strong acid or super strong acid, (a) mercury, (b) carbon monoxide and (c) oxidation What reacted the agent may be used. As the mercury catalyst, the latter is preferable because of its higher catalytic activity.

The reaction temperature for reacting the mercury catalyst with carbon monoxide or the like in a strong acid or super strong acid in advance is not particularly limited, and may be room temperature. The reaction temperature is generally -10 to 70
C., and preferably about 5 to 40 C. The partial pressure of carbon monoxide is not particularly limited, and is generally about 0.1 to 10 atm, preferably 0.5 atm, as the carbon monoxide partial pressure.
About 5 atm. In this reaction, the carbon monoxide partial pressure is 1
It progresses even if it is lower than the atmospheric pressure. The reaction may be carried out in the presence of an inert gas such as nitrogen or argon, or proceeds in the presence of air or oxygen. The reaction time is generally about 2 hours to 3 days, preferably about 1 day to 2 days. The prepared mercury carbonyl may be used after being isolated, but the prepared liquid may be used without isolation. In addition, the mercury catalyst of the present invention exhibits sufficient catalytic activity when used alone without being used in combination with another catalyst, but may be used in combination.

At least one compound selected from the group consisting of olefins and alcohols is reacted in a strong acid in the presence of the mercury catalyst of the present invention, and then tertiary carboxylic acid is obtained by adding water.

In the present invention, the olefin used as a raw material for synthesizing a tertiary carboxylic acid or an ester thereof is not particularly limited as long as it is an aliphatic unsaturated hydrocarbon having 4 or more carbon atoms and having at least one double bond. The olefin of the present invention
For example, it may have an annular structure. The number of double bonds in the olefin is not particularly limited, but is usually 1 to
6, preferably 1-4, particularly preferably 1-2.

Among the olefins of the present invention, for example, compounds having one double bond include:

[0029]

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[Wherein, R ^a , R ^b , R ^c and R ^d are the same or different and each represents a hydrogen atom, a linear alkyl group, a branched alkyl group or a cyclic alkyl group. Or ^Ra and ^Rb
And / or R ^c and R ^d may together form a cyclic alkyl group. Alternatively, ^Ra and ^Rc may together form a cyclic alkene. The cyclic alkyl group and cyclic alkene may be substituted with one or more C _1-6 linear or branched alkyl groups. Where R ^a , R ^b ,
The total number of carbon atoms of R ^c and R ^d is 2 or more. ] Is shown.

Specifically, 1-butene, 2-butene, 1
- hexene, hexene 2-ethyl-1, 1-octene, 1-nonene, 1-decene, butene dimer, butene trimers, butene tetramer, propylene dimers, linear and propylene trimer or branched C _{4- 50} terminal or internal olefins, and 3-cyclohexyl-1-butene, 3-cyclohexyl-2-butene,
-Cyclopentyl-1-butene, 4-cyclopentyl-
A terminal olefin or an internal olefin having a C _4-10 cyclic alkyl group which may be substituted by a C _1-6 linear or branched alkyl such as 2-butene, 1-vinyl-4-methylcyclohexane, and cyclohexene; C _4-10 which may be substituted by C _1-6 linear or branched alkyl such as 1-methylcyclohexene, cyclooctene and the like.
And cyclic alkenes.

Alcohol (ROH) used as a raw material for the synthesis of tertiary carboxylic acid or its ester in the present invention
Is not particularly limited as long as it is an alcohol having 1 or more hydroxyl groups and 4 or more carbon atoms. As the alcohol, all alcohols such as primary alcohol, secondary alcohol, tertiary alcohol and cyclic alcohol can be used. The number of hydroxyl groups in the alcohol is not particularly limited,
Usually 1-6, preferably 1-4, particularly preferably 1-2
It is. For example, among the alcohols having one hydroxyl group, ROH [where R is a straight-chain alkyl group, a branched alkyl group, a straight-chain or branched alkyl group having 4 or more carbon atoms] Represents any of the optionally substituted cyclic alkyl groups. And primary, secondary and tertiary alcohols represented by the formula:

Specifically, 1-butanol, 2-butanol, 1-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 1-hexanol,
1-heptanol, 1-octanol, 2-methyl-1
Linear or branched C _4-50 primary alcohols such as hexanol, 1-decanol, 1-nonyl alcohol, 1-dodecanol, and substituted C _4-10 cyclic alkyls thereof, 2-pentanol, Linear or branched C _4-50 secondary alcohols such as monohexanol, 2-heptanol, 2-octanol, 2-dodecanol and the like;
_4-10 cyclic alkyl substituents, C _4-50 such as 2-methyl-2-propanol, 2-methyl-2-butanol, 3-methyl-3-heptanol, 3-methyl-3-hexanol
Tertiary alcohols and their C _4-10 cyclic alkyl substituents, and C _4-10 cyclic alcohols such as cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol and their C _1-6
Alkyl substituents.

In the presence of the mercury catalyst of the present invention, in a strong acid, at least one compound selected from the group consisting of olefins and alcohols is reacted, and then water is added to obtain a reaction (formula (I)). 2) is considered to proceed as follows. Olefins give carbocations by protonation in strong acids. On the other hand, alcohol (ROH) gives a carbocation through a dehydration reaction following proton addition. Carbocations formed from olefins or alcohols areomerize to tertiary carbocations. The resulting tertiary carbocation is
Reacts with water and carbon monoxide to give tertiary carboxylic acids.

[0035]

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Wherein R ^a , R ^b , R ^c , R ^d and R are as defined above. R ¹ , R ² and R ³ are the same or different and each represents a linear alkyl group, a branched alkyl group or a cyclic alkyl group, or R ¹ and R ² are bonded to form a cyclic alkyl group; May be formed. The cyclic alkyl group is
It may be substituted by a C _1-6 linear or branched alkyl group. R ⁴ represents a linear alkyl group, a branched alkyl group,
It indicates any of the cyclic alkyl groups which may be substituted with a linear or branched alkyl group. In the above reaction, when the tertiary carbocation is reacted with an alcohol (R ⁴ OH) instead of water, a tertiary carboxylic acid ester is obtained (formula 3).

In the present invention, as the alcohol (R ⁴ OH) used for synthesizing the tertiary carboxylic acid ester, all alcohols such as primary alcohol, secondary alcohol, tertiary alcohol and cyclic alcohol can be used. For example, R ⁴ represents any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group which may be substituted with a linear or branched alkyl group. As R ⁴ , specifically, a linear or branched C _1-15 alkyl such as methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, cycloheptyl, cyclooctyl, etc. And C _4-10 cyclic alkyl groups such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and C _1-6 alkyl-substituted groups thereof. As R ⁴ , among these, a linear or branched C _1-3 alkyl group is preferable. In the method for synthesizing the tertiary carboxylic acid ester of the present invention, when alcohol (ROH) is used as a raw material, the starting alcohol
(ROH) and added at the end of the reaction alcohol (R ⁴ OH)
Does not matter whether it is the same kind of compound.

The strong acid used in the method for synthesizing the tertiary carboxylic acid or its ester and the reaction between the mercury catalyst and carbon monoxide of the present invention are not particularly limited as long as they are strong acids. For example, sulfuric acid, sulfuric acid-phosphoric acid, hydrofluoric acid, FSO ₃ H,
Boron trifluoride, trifluoromethanesulfonic acid and the like can be used alone or in combination of two or more. The concentration of these strong acids is not particularly limited, but is preferably high. The concentration of the strong acid is usually about 70% or more, preferably about 80% or more, and more preferably about 95% or more. These strong acids are necessary for the generation of catalytically active species, but are also necessary for generating or stabilizing a carbocation as a reaction intermediate.

In the method for synthesizing a tertiary carboxylic acid or an ester thereof of the present invention, at least one selected from the group consisting of a diene, a diol, and a compound having at least one double bond and at least one hydroxyl group is used as the olefin or alcohol as a raw material for the synthesis. When one kind is used, a tertiary dicarboxylic acid or an ester thereof is obtained. That is,
In the presence of the mercury catalyst of the present invention, in a strong acid, at least one compound selected from the group consisting of a diene, a diol, and a compound having one double bond and one hydroxyl group,
By reacting carbon monoxide and then adding water, a tertiary dicarboxylic acid can be obtained. Further, in the presence of the mercury catalyst of the present invention, in a strong acid, at least one compound selected from the group consisting of a diene, a diol, and a compound having one double bond and one hydroxyl group, is reacted with carbon monoxide. Addition of an alcohol (R ⁴ OH) gives a tertiary dicarboxylic acid ester.

The diene used as a raw material for synthesizing a tertiary dicarboxylic acid or an ester thereof has 8 or more carbon atoms and has a double bond at each of carbon atoms separated by 5 or more CC bonds. The number is not particularly limited as long as it is a diene having a number of 8 or more and having a cyclic structure. These dienes can be used alone or in combination of two or more. C 8 or more and 5 or more C—C
Examples of the diene having a double bond at each carbon separated from the bond include, for example, a linear or branched C such as 1,7-octadiene, 1,9-decadiene, 1,11-dodecadiene, and 1,12-tridecadiene. _8-50 dienes and the like. As the diene having 8 or more carbon atoms and having a cyclic structure, a diene having a cyclic alkylene moiety such as limonene may be used.
_And cyclic alkyl adducts of _8-50 dienes and straight-chain or branched C _8-50 dienes.

The diol used as a raw material for synthesizing a tertiary dicarboxylic acid or an ester thereof is not particularly limited as long as it has 8 or more carbon atoms and has a hydroxyl group on each of carbon atoms separated by 6 or more CC bonds. Not done. Examples of the diol having 8 or more carbon atoms and having a hydroxyl group on each of carbon atoms separated by 6 or more CC bonds include, for example, 1,8
-Octadiol, 1,10-decanediol, 1,1
2-dodecanediol, 2,9-dimethyldecane-2,
Linear or branched _C8-50 diols such as 9-diol,
C _8-50 diols having a cyclic alkyl such as 5-cyclooctadiol and 1,6-cyclodecanediol are _exemplified . These diols can be used alone or in combination of two or more.

The compound having at least one double bond and at least one hydroxyl group used as a raw material for synthesizing a tertiary dicarboxylic acid or an ester thereof is not particularly limited as long as it has one double bond and one hydroxyl group. A hydroxyl group and / or a carbon atom having 8 or more carbon atoms separated by 5 or more CC bonds;
Alternatively, a compound having a double bond is preferable. The number of double bonds and hydroxyl groups in the compound is not particularly limited, but usually has a total of 6 or less, preferably 4 or less, and particularly preferably one double bond and one hydroxyl group. For example, linear or branched _C8-50 compounds such as 7-octen-1-ol, 7-octen-2-methyl-1-ol, 8-nonen-1-ol and 9-decen-1-ol. , 4-
_C8-50 compounds having a cyclic alkyl such as (1-propenyl) -cyclohexane-1-ol and the like. These compounds may be used alone or in combination of two or more.

In the method for synthesizing a tertiary carboxylic acid or an ester thereof using a mercury catalyst of the present invention, a saturated hydrocarbon compound may be used as a raw material. That is, in the presence of the mercury catalyst of the present invention, in a strong acid, in the presence of an alcohol or an olefin, at least one saturated hydrocarbon compound is reacted with carbon monoxide, and then water is added to form a tertiary carboxylic acid. Can be obtained. Further, in the presence of the mercury catalyst of the present invention, at least one saturated hydrocarbon compound is reacted with carbon monoxide in the presence of an alcohol or olefin in a strong acid, and then the alcohol (R ⁴
By adding OH), a tertiary carboxylic acid ester can be obtained.

It is considered that the synthesis reaction of the tertiary carboxylic acid using a saturated hydrocarbon as a raw material proceeds as follows. A saturated hydrocarbon compound having a tertiary hydrogen is extracted with a tertiary hydrogen in a strong acid in the presence of an olefin or an alcohol to give a tertiary carbocation. this is,
This is because the carbocation generated from the olefin or the alcohol extracts the tertiary hydrogen of the saturated hydrocarbon. Tertiary carbocations generated from saturated hydrocarbon compounds react with carbon monoxide and water under a mercury catalyst to give tertiary carboxylic acids. Equation 4 shows a reaction formula in the case where, for example, methylcyclohexane is used as the saturated hydrocarbon.

[0045]

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[In the formula, R ⁺ represents a carbocation generated from an olefin or alcohol to be coexisted. The saturated hydrocarbon compound used as a raw material for the synthesis of the tertiary carboxylic acid or its ester is not particularly limited as long as it is a saturated hydrocarbon compound having tertiary hydrogen and having 4 or more carbon atoms. For example,

[0047]

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[Wherein R ¹ , R ² and R ³ are the same or different and each represents a linear alkyl group, a branched alkyl group or a cyclic alkyl group, or R ¹ and R 2 ² may combine to form a cyclic alkyl. ].

Specifically, a branched C _4-50 saturated hydrocarbon compound such as t-butane, a C _4-10 cyclic saturated compound such as methylcyclohexane, methylcyclopentane, ethylcyclohexane, ethylcyclopentane, methylcyclooctane, etc. And C _1-6 alkyl substituents of hydrocarbon compounds.

The olefin or alcohol coexisting in the above reaction is not particularly limited as long as it forms a carbocation in a strong acid, but it has 4 or more carbon atoms and forms a tertiary carbocation. Is preferred.

When a saturated hydrocarbon compound is used as a raw material for the synthesis of a tertiary carboxylic acid, a super strong acid may be used instead of a strong acid. In this case, there is no need to make alcohol or olefin coexist. That is, in the presence of the mercury catalyst of the present invention, a tertiary carboxylic acid can be obtained by reacting carbon monoxide with at least one unsaturated hydrocarbon compound in a superacid and then adding water. it can.

The superacid used in the tertiary carboxylic acid or ester synthesis method of the present invention and the reaction between the mercury catalyst and carbon monoxide is not particularly limited as long as it is a superacid. A super strong acid is an acid having an acidity stronger than 100% sulfuric acid. For example, at least one Lewis acid such as SbF ₅ (antimony pentafluoride) or SO ₃ (sulfur trioxide) is added to a compound in which one hydroxyl group of sulfuric acid is substituted with an electron-withdrawing atom or group, if necessary. Acid, sulfuric acid-sulfur trioxide (fuming sulfuric acid) and the like. Specifically, sulfuric acid-sulfur trioxide, ClSO
₃ H, 100% FSO ₃ H, FSO ₃ H-SO ₃ , FSO _{3
H-SbF 5, HF-SbF} 5 , and the like.

When a tertiary carboxylic acid is synthesized using a super strong acid, the bond of the alkyl main chain of the carbocation formed from the saturated hydrocarbon is broken during isomerization to a tertiary carbocation. In some cases (Example 6).

In order to clarify the effect of the mercury catalyst in the present invention, the effect of the addition of the mercury catalyst in the carboxylation reaction of 1-hexene is shown in Table 1. The reaction is sulfuric acid 10
A predetermined amount of a mercury catalyst was added to each ml, the air was replaced with 1 atm of carbon monoxide, and the mixture was vigorously stirred. Then, 1-hexene (5 mmol) was gradually added at 25 ° C. to cause a reaction.

[0055]

[Table 1]

As is evident from Table 1, the addition of the mercury catalyst accelerated the carbonylation reaction and resulted in a higher yield of tertiary C ₇ than in the absence of the mercury catalyst.
The carboxylic acid (2: 1 mixture of 2,2-dimethylpentanoic acid and 2-methyl-2-ethylbutanoic acid) was obtained.

The method for synthesizing the tertiary carboxylic acid or its ester according to the present invention can be carried out, for example, as follows. A strong acid or super strong acid and a mercury catalyst are placed in a sealable reaction vessel, air is exhausted by a vacuum pump, carbon monoxide is introduced, and the mixture is vigorously stirred to form mercury carbonyl. At this time, the reaction does not hinder even if air remains. When mercury carbonyl is formed in a super-strong acid and a tertiary carboxylic acid or its ester is synthesized in the strong acid, the mercury carbonyl solution may be diluted with water to a strong acid. When a predetermined tertiary carboxylic acid synthesis raw material such as olefin is gradually added to the catalyst solution, it reacts with carbon monoxide. When the reaction mixture is added to ice water, a tertiary carboxylic acid is obtained, and an alcohol (R ⁴
The addition of (OH) gives the ester of a tertiary carboxylic acid. The product can be extracted and separated by an organic solvent such as hexane, benzene, methylcyclohexane, monochlorobenzene, chloroform, carbon tetrachloride or the like according to a conventional method.

The synthesis reaction of the tertiary carboxylic acid or its ester of the present invention proceeds sufficiently at normal temperature and normal pressure. Further, the reaction proceeds even in the presence of oxygen or air, or even when the pressure of carbon monoxide is reduced. Although the carbon monoxide partial pressure is not particularly limited, it is generally 0.1 to 1 as carbon monoxide partial pressure.
The pressure is about 0 atm, preferably about 0.5 to 5 atm. When the partial pressure of carbon monoxide is low due to the coexistence of air and other gases, pressurization can accelerate the reaction rate and improve the yield.

The reaction temperature is not particularly limited, but is generally about -10 to 70 ° C, preferably 5 to 40 ° C.
It is about. The reaction time can be appropriately set depending on the type of the mercury catalyst used, the type of the strong acid including the super strong acid, the reaction temperature, and the like. The reaction time is generally 3 hours or less, preferably 10 minutes to 2 hours, more preferably 30 minutes to 1 hour.

[0060]

According to the present invention, a tertiary carboxylic acid and an ester thereof can be produced by using a mercury catalyst.
Can be obtained selectively.

[0061]

EXAMPLES In the following, various experiments were conducted to explain the present invention in more detail. The present invention is not limited to these examples.

Example 1 Tertiary Carboxy from Olefin
To the three Rrofurasuko volume 200ml connected synthesis gas burette acid, 96% sulfuric acid 10m1 and mercury sulfide (II) 465 mg (2 mmol) was added, was evacuated by a vacuum Ponbu one at 25 ° C., 1 atm Carbon oxide was introduced and stirred vigorously. By using a gas buret, the reaction system was always kept at 1 atm of carbon monoxide. Then, 0.62 ml (5 mmol) of 1-hexene was gradually added to the catalyst solution, and after 30 minutes, 40 ml (about 1.79 mmol) of carbon monoxide reacted with 1-hexene. The reaction mixture was added to ice water, and the product was extracted twice with n-hexane.
The product was identified as a 2: 1 mixture of 2,2-dimethylpentanoic acid and 2-methyl-2-ethylbutanoic acid by gas chromatography, NMR (having the same chemical shift value as a commercial product), IR, and GC-MS analysis. . The total yield of the mixture was
Titration with 1 N NaOH solution gave 35% (1.7
5 mmol). By applying carbon monoxide partial pressure,
An improvement in yield was seen.

Example 2 Alcohol to Tertiary Carboxyl
A mercury (II) sulfate (593.2 mg, 2 mmol) and 96% sulfuric acid (10 ml) were added to a 200-ml three-neck flask connected to an acid syngas burette, and the air was evacuated.
Carbon monoxide was introduced at 25 ° C. and 1 atm and stirred vigorously. Then, 1-octanol 0.7 was added to the catalyst solution.
When 9 ml (5 mmol) was gradually added, 57 ml (2.
54 mmol) of carbon monoxide was absorbed. The reaction mixture was added to ice water, and the product was extracted with n-hexane.
The product was analyzed by GC, NMR (chemical shift value is the same as that of a commercially available product), IR and GC-MS to find 2,2-dimethylheptanoic acid: 2-methyl-2-ethylhexanoic acid:
It was identified as a 4: 2: 1 mixture of 2-methyl-2-propylpentanoic acid. The total yield of the mixture is 0.1N NaO
Titration with H solution gave 50% (2.5 mmol).

Example 3 Olefin to Tertiary Carboxyl
After purging a 200 ml capacity flask connected to a synthetic gas burette of an acid ester with carbon monoxide, mercury (I) sulfate 49
7.2 mg (1 mmol) and 5 ml of 95% hydrogen fluoride were added and stirred vigorously. Then, 112 ml (5 mmol) of 1-butene was added through a gas burette,
43 ml (1.92 mmol) of carbon monoxide had reacted. After completion of the reaction, 3 ml of methanol was added to form a methyl ester, and hydrogen fluoride was distilled off. The product was extracted with hexane and analyzed by GC, NMR (chemical shift value is the same as that of a commercial product), IR, etc., and as a result, 37% (1.85 mmol) of piperic acid methyl ester was obtained. Was revealed.

Example 4 Diene to Tertiary Dicarboxylic Acid
Of a 200 ml synthetic flask with carbon monoxide (1 atm)
After that, 637 mg (2 mmol) of mercury acetate (II) and 10 ml of boron trifluoride / water complex (1: 1) were added, and the mixture was vigorously stirred. Then, 1,11
1.1 ml (5 mmol) of dodecadiene were slowly added and reacted with 96 ml of carbon monoxide. The reaction mixture was added to ice water, and the product was extracted with benzene. The product is NM
R, was analyzed by IR, was tertiary C ₁₄ carboxylic acid mainly composed of 2,2,9,9- tetramethyl-decanedicarboxylic acid. One-fifth of the product is 0.1N Na
The yield was determined by titration with OH solution (42%).

Example 5: Tertiary dicarboxylic acid from diol
After replacing a three-neck flask with a synthetic capacity of 200 ml of acid with carbon monoxide, 519.2 mg (2 mmol) of mercury (I) acetate,
7 ml of 96% concentrated sulfuric acid and 3 ml of 99% fluorosulfuric acid were added and stirred vigorously. Then, 1,12
1.12 ml (5 mmol) of dodecanediol are added and reacted with 125 ml of carbon monoxide. The reaction was added to ice water, the product extracted with benzene, and the product was characterized by NMR (consistent with literature values, Y. Souma et al. Bull. Chem. Soc. Jpn.,
1976, 49 , 3291).
It was a tertiary C ₁₄ carboxylic acid containing mainly 9,9-tetramethyldecanedicarboxylic acid. The yield was determined by titrating 1/5 of the product with 0.1N NaOH solution (55%).

Example 6: Saturated hydrocarbon in super strong acid
To a 200-ml three-necked flask connected to a synthetic gas burette of tertiary carboxylic acid, and 401 mg (2 mmol) of mercury and 10% of 96% sulfuric acid.
Then, after the inside of the flask was replaced with carbon monoxide, 3 g of sulfur trioxide (SO ₃ ) was added, followed by vigorous stirring. Then
To this catalyst solution was gradually added 0.81 ml (5 mmol) of octane, and reacted with 110 ml of carbon monoxide. The reaction mixture was added to ice water, and the product was extracted with n-hexane. The product was analyzed by gas chromatography, NMR (corresponding to the chemical shift value of a commercial product), and IR.
The yield is 98 mol% based on octane by titration with 0.1 N NaOH solution.
It became clear that it was.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 53/126 C07C 53/126 67/36 67/36 67/38 67/38 69/24 69/24 // C07B 61/00 300 C07B 61/00 300 (56) Reference JP-A-51-59812 (JP, A) JP-A-56-97245 (JP, A) JP-A-10-59893 (JP, A) JP-A 10-237010 (JP, A) U.S. Pat. No. 3,316,290 (US, A) U.S. Pat. No. 2,864,858 (US, A) WO 96/10006 (WO, A1) Bull. Chem. Soc. Jpn. , 49 [11] (1976), 3296-3299. (58) Fields investigated (Int. Cl. ⁶ , DB name) C07C 51/12 C07C 51/10 C07C 51/14 C07C 53/126 C07C 67/36 C07C 67/38 C07C 69/24 CAPLUS (STN) REGISTRY (STN) WPIDS (STN)

Claims (13)

(57) [Claims] (1) in a strong acid, at least one compound selected from the group consisting of olefins and alcohols,
By reacting carbon monoxide and then adding water,
A method for synthesizing a tertiary carboxylic acid, wherein the reaction is carried out in the presence of a mercury catalyst. 2. In a strong acid, at least one compound selected from the group consisting of olefins and alcohols,
A method for synthesizing a tertiary carboxylic acid ester by reacting carbon monoxide and then adding an alcohol, wherein the reaction is carried out in the presence of a mercury catalyst. 3. A method comprising reacting carbon monoxide with a strong acid in at least one compound selected from the group consisting of a diene, a diol, and a compound having at least one double bond and one hydroxyl group, and then adding water. The method for synthesizing a tertiary dicarboxylic acid according to the above, wherein the reaction is carried out in the presence of a mercury catalyst. 4. In a strong acid, carbon monoxide is allowed to react with at least one compound selected from the group consisting of a diene, a diol, and a compound having at least one double bond and one hydroxyl group, and then an alcohol is added. A method for synthesizing a tertiary dicarboxylic acid ester, wherein the reaction is carried out in the presence of a mercury catalyst. 5. In a strong acid, at least one saturated hydrocarbon compound is added in the presence of an alcohol or an olefin,
By reacting carbon monoxide and then adding water,
A method for synthesizing a tertiary carboxylic acid, wherein the reaction is carried out in the presence of a mercury catalyst. 6. In a strong acid, in the presence of an alcohol or an olefin, at least one saturated hydrocarbon compound is
A method for synthesizing a tertiary carboxylic acid ester by reacting carbon monoxide and then adding an alcohol, wherein the reaction is carried out in the presence of a mercury catalyst. 7. The method according to claim 1, wherein the strong acid is at least one selected from the group consisting of sulfuric acid, sulfuric acid-phosphoric acid, hydrofluoric acid, FSO ₃ H, boron trifluoride and trifluoromethanesulfonic acid. Item 7. The synthesis method according to any one of Items 1 to 6. 8. A method for synthesizing a tertiary carboxylic acid by reacting carbon monoxide with at least one saturated hydrocarbon compound in a super strong acid and then adding water, wherein the reaction is carried out using a mercury catalyst. A method for synthesizing a tertiary carboxylic acid, which is carried out in the presence. 9. The super strong acid is sulfuric acid-sulfur trioxide, ClSO ₃
H, 100% FSO ₃ H, FSO ₃ H—SO ₃ , FSO ₃ H
Synthesis of claim 8, wherein the at least one selected from the group consisting of -SbF ₅ and HF-SbF _5. 10. A mercury catalyst comprising: mercury sulfate (I, II), mercury acetate (I, II), mercury fluoride (I), mercury oxide (II),
2. The method according to claim 1, wherein the at least one element is selected from the group consisting of mercury (II) hydroxide and mercury (II) sulfide.
10. The synthesis method according to any one of claims 1 to 9. 11. The method according to claim 1, wherein the mercury catalyst is at least one selected from the group consisting of (a) mercury and (b) SO ₃ and S ₂ O ₆ F ₂ . Synthetic method described in 1. 12. A mercury catalyst, which has been previously prepared in a strong acid or super strong acid, is prepared by: (a) mercury sulfate (I, II);
Prepared from at least one mercury compound selected from the group consisting of I), mercury fluoride (I), mercury oxide (II), mercury hydroxide (II), and mercury (II) sulfide; and (b) carbon monoxide. The synthesis method according to any one of claims 1 to 9, wherein: 13. A mercury catalyst, which has been prepared in advance in a strong acid or a super-strong acid, is (a) mercury, (b) carbon monoxide and (c) SO ₃ and S _3.
The method according to claim 1, wherein the method is prepared from at least one selected from the group consisting of ₂ O ₆ F ₂ .