JP2014196286A - Method of producing organic compound by dehydration condensation reaction in water - Google Patents

Abstract

The present invention provides a high-efficiency, novel surfactant-type catalyst for dehydration-condensation in water, which has been difficult to put into practical use due to the slow reaction rate of conventional catalysts. To provide a condensation reaction method. SOLUTION: Dehydration condensation reaction such as ester formation reaction by reaction of carboxyl group and hydroxy group, ether formation reaction by reaction of hydroxy group and hydroxy group, thioether formation reaction by reaction of hydroxy group and mercapto group Is carried out in water, when at least one of the reaction substrates is a hydrophobic compound, the compound represented by the general formula (I) (wherein R1 and R2 each represents a linear or branched alkyl group having 6 to 30 carbon atoms, R1 and R2 may be the same or different, and n is 0 or an integer of 1 to 3). [Selection] Figure 1

Description

  The present invention relates to a method for producing an organic compound by dehydration condensation reaction in water. More specifically, the present invention relates to a method for producing an organic compound that efficiently performs a dehydration condensation reaction in water using a surfactant-type catalyst.

In recent years, organic chemical reactions in water have attracted attention from the viewpoint of environmentally friendly green chemistry. The organic reaction in water is expected as a technology that leads to environmental load reduction such as waste reduction and efficient use of energy.
An industrially important organic chemical reaction is a dehydration condensation reaction, and it has been conventionally difficult to carry out this in water. For example, since the esterification reaction of carboxylic acid and alcohol, which is a typical dehydration condensation reaction, is an equilibrium reaction, the reaction is carried out while removing the generated water by adding a dehydrating agent or azeotropically, or one reaction substrate is removed. Equilibrium is biased toward the product side by using a large excess. If water is present in the reaction system, it is disadvantageous for the reaction equilibrium, so that it is generally not preferable to perform the esterification reaction in the presence of water.

  As a method for performing a dehydration condensation reaction in water, Patent Documents 1 to 3 and Non-Patent Documents 1 to 3 disclose a method using a Bronsted acid having a surfactant structure as a catalyst (J. Am. Chem. Soc). , 123, 10101 to 10102 (2001); Non-Patent Document 1, J. Am. Chem. Soc., 124, 11971 to 11978 (2002), Non-Patent Document 2, Chem. Lett., 35, 238 to 239 ( 2006); Non-Patent Document 3, JP-A 2003-55302; Patent Document 1, JP-A 2003-267899; Patent Document 2, JP-A 2006-232811, Patent Document 3). In this method, by using dodecylbenzenesulfonic acid as a catalyst, the reaction proceeds inside the emulsion formed in water, and esterification, etherification, thioetherification, glycosidic bond formation reaction and the like in water are possible. However, the dehydration condensation reaction in water using these surfactant type catalysts has a problem that the reaction rate is slower than the reaction in an organic solvent, and the reaction takes a long time. An increase in reaction time leads to an increase in production cost, and thus high activation of the catalyst has been a major issue for industrialization. Further, various types of surfactant type catalysts have been developed so far, but detailed examination of catalyst structure and reaction activity has not been performed. For example, in the case of an alkylbenzenesulfonic acid type catalyst, it has been considered that the structure of the alkyl group has little influence on the reaction as long as it has a certain number of carbon atoms or more.

Japanese Patent Laid-Open No. 2003-55302 JP 2003-267899 A JP 2006-232811 A

J. et al. Am. Chem. Soc. , 123, 10101-10102 (2001) J. et al. Am. Chem. Soc. , 124, 11971-111978 (2002) Chem. Lett. , 35, 238-239 (2006)

  An object of the present invention is to provide a highly efficient novel surfactant-type catalyst in a dehydration condensation reaction in water, which has been difficult to put into practical use due to the slow reaction rate of conventional catalysts, and has high yield and high selectivity. Another object of the present invention is to provide a method for dehydration condensation reaction in water.

  As a result of intensive studies to solve the above problems, the present inventors have succeeded in developing a highly active novel surfactant-type catalyst by optimizing the structure of the alkyl group of alkylbenzene sulfonic acid, It was found that the reaction rate was remarkably improved as compared with the conventional catalyst, and the present invention was completed.

That is, this invention relates to the manufacturing method of the organic compound of the following [1]-[8].
[1] In a method for producing an organic compound by dehydration condensation in water between reaction substrates in which at least one of the reaction substrates is a hydrophobic compound, the general formula (I)
(In the formula, R ¹ and R ² represent a linear or branched alkyl group having 6 to 30 carbon atoms, R ¹ and R ² may be the same or different, and n is 0, or 1 to 3; A method for producing an organic compound, which comprises using a surfactant-type catalyst represented by the following formula:
[2] The method for producing an organic compound according to item ^1, wherein R ¹ and R ^{2 in} the general formula (I) each independently represent a linear or branched alkyl group having 8 to 20 carbon atoms.
[3] R ¹ and R ^{2 in} the general formula (I) are each independently a linear alkyl group having 8 to 14 carbon atoms or an alkyl group having 10 to 16 carbon atoms having one branch, A method for producing the organic compound.
[4] The method for producing an organic compound according to any one of items 1 to 3, wherein n in the general formula (I) is 0 or 1.
[5] The method for producing an organic compound as described in any one of [1] to [4], wherein the reaction substrates are all hydrophobic compounds.
[6] The method for producing an organic compound according to any one of items 1 to 5, wherein the dehydration condensation reaction is any of an esterification reaction, an etherification reaction, and a thioetherification reaction.
[7] The method for producing an organic compound according to item 6, wherein the dehydration condensation reaction is an esterification reaction.
[8] The method for producing an organic compound according to item 7, wherein the dehydration condensation reaction is an esterification reaction of an alcohol having 4 to 30 carbon atoms and a carboxylic acid having 4 to 30 carbon atoms.

  According to the method for producing an organic compound of the present invention using a catalyst in which the structure of the alkyl group of alkylbenzene sulfonic acid is optimized, dehydration condensation in water is more efficient than the conventional method using a linear alkylbenzene sulfonic acid catalyst. Since the reaction becomes possible, the reaction time can be greatly shortened, leading to a reduction in production cost. The dehydration condensation technique in water can also be applied to a technique for recovering organic substances such as alcohol and carboxylic acid contained in water.

It is a graph which shows the relationship between the reaction time and yield in the underwater esterification reaction in Examples 1-4 and Comparative Examples 1-2 using various surfactant type catalysts.

  Hereinafter, preferred embodiments of the present invention will be described in detail, but the present invention is not limited to these embodiments, and various applications are possible within the scope of the claims.

1. Dehydration condensation reaction The dehydration condensation reaction in the present invention is a reaction in which two functional groups react, water is eliminated, and the two functional groups are bonded. Specific examples include an ester formation reaction by a reaction between a carboxyl group and a hydroxy group, an ether formation reaction by a reaction between a hydroxy group and a hydroxy group, and a thioether formation reaction by a reaction between a hydroxy group and a mercapto group. Among these, the esterification reaction is most preferable from the viewpoint of industrial utility.
The dehydration condensation reaction in water in the present invention is a reaction performed in the presence of an excess amount of water (for example, 1 mass times or more) with respect to at least one of the reaction substrates in the dehydration condensation reaction.

2. Catalyst In the present invention, a surfactant type Bronsted acid catalyst is used. By using a surfactant-type catalyst, the reaction substrate is taken into the micelle to form a stable emulsion in water. The inside of the emulsion is a hydrophobic reaction field, and water generated by the dehydration condensation reaction is quickly eliminated from the inside of the emulsion, so that the equilibrium is inclined toward the product.

In the present invention, the surfactant-type Bronsted acid catalyst is represented by the general formula (I)
(In the formula, R ¹ and R ² represent a linear or branched alkyl group having 6 to 30 carbon atoms, R ¹ and R ² may be the same or different, and n is 0, or 1 to 3. is there.)
The alkylbenzene sulfonic acid shown by these is used as a catalyst. By introducing a long-chain alkyl group with a branched structure on the benzene ring, the affinity with the substrate is significantly improved compared to a linear alkylbenzene sulfonic acid without branching, and a more stable hydrophobic reaction field is constructed. Is possible. R ¹ and R ² are more preferably a linear or branched alkyl group having 8 to 20 carbon atoms from the viewpoint of the fat solubility of the catalyst and the stability of the emulsion. If the number of carbon atoms in the alkyl group is too large, the catalyst synthesis becomes complicated and the catalyst cost increases. From the balance of catalyst activity and cost, R ¹ and R ² are most preferably a linear alkyl group having 8 to 14 carbon atoms or an alkyl group having one branch having 10 to 16 carbon atoms. The value of n is preferably 0 or 1 from the viewpoint of catalyst synthesis.

Specifically, an alkylbenzene sulfonic acid represented by the following formula (1) (in formula (I), n = 1, R ¹ , R ² = C12, abbreviated as C26 four-branched alkyl benzene sulfonic acid), in formula (2) Alkylbenzenesulfonic acid represented by formula (I) (n = 1, R ¹ , R ² = C8, abbreviated as C18 four-branched alkylbenzenesulfonic acid), alkylbenzenesulfonic acid represented by formula (3) (n in formula (I) = 0, R ¹ = C12, R ² = C11, C24 abbreviated as bi-branched alkylbenzene sulfonic acid) and alkylbenzene sulfonic acid represented by formula (4) (in formula (I), n = 0, R ¹ = C9, R ² = C8, C18, which is abbreviated as bi-branched alkyl benzene sulfonic acid), is more preferable.

3. Reaction Substrate The reaction substrate used in the reaction of the present invention has a functional group that performs a dehydration condensation reaction, and at least one is a hydrophobic compound. Furthermore, it is desirable that the two substrates that perform the dehydration condensation reaction are hydrophobic. From the viewpoint of forming a stable emulsion, it is more preferable that all reaction substrates are hydrophobic compounds. The hydrophobic compound in the present invention is an organic compound having a solubility in water of less than 200 g / L at 1 atm and 20 ° C. Among these hydrophobic compounds, those having 4 to 30 carbon atoms are more preferable as the reaction substrate, and most preferably those having 6 to 20 carbon atoms.

The compound having a carboxyl group (that is, a carboxylic acid) in the reaction for forming an ester by dehydration condensation reaction between a carboxyl group and a hydroxy group is preferably one having 4 to 30 carbon atoms and 6 to 20 carbon atoms in view of hydrophobicity. Is preferred. Specific examples include valeric acid, isovaleric acid, 2-methylbutyric acid, pivalic acid, hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, Saturated carboxylic acids such as margaric acid, stearic acid, cyclohexane acid, unsaturated carboxylic acids such as oleic acid, linoleic acid, linolenic acid, arachidonic acid, docosahexaenoic acid, eicosapentaenoic acid, benzoic acid, salicylic acid, cinnamic acid, phenylacetic acid And aromatic carboxylic acids such as phenylpropionic acid, dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, isophthalic acid and terephthalic acid.
As a compound (namely, alcohol) which has a hydroxyl group, a C4-C30 thing is preferable from a hydrophobic surface, and C6-C20 is preferable. Specific examples include 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol. 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 1-nonadecanol, 1-eicosanol, 1-heneicosanol, 1-docosanol, 1-tetracosanol, Saturated alcohol having a linear structure such as 1-hexacosanol, iso-butanol, sec-butanol, tert-butanol, 2-octanol, 2-ethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol Has a branched chain structure such as 2-octyl-1-dodecanol Saturated alcohols, saturated alcohols having an alicyclic structure such as cyclohexanol, trans-2-dodecen-1-ol, trans-2-tridecen-1-ol, trans-9-octadecen-1-ol, oleyl alcohol, cis , Cis-9,12-octadecadien-1-ol, unsaturated alcohols such as cis-13-docosen-1-ol, benzyl alcohol, 1-phenylethyl alcohol, 2-phenylethyl alcohol, 3-phenylpropanol, Examples include alcohols having an aromatic ring such as diphenylcarbinol and polyhydric alcohols such as pentaerythritol. In addition, compounds having a carboxyl group and a hydroxy group in the molecule, such as glycolic acid, lactic acid, 2-hydroxybutyric acid, and 3-hydroxybutyric acid can also be used.

Examples of the compound having a hydroxy group in a reaction for producing a thioether by a dehydration condensation reaction between a hydroxy group and a mercapto group include the alcohols described above.
As a compound (namely, thiol) which has a mercapto group, a C3-C20 thing is preferable and 6-18 are more preferable. Specific examples include 1-propanethiol, 2-propanethiol, 1-butanethiol, 2-butanethiol, 2-methyl-2-propanethiol, 1-hexanethiol, 1-octanethiol, 1-decanethiol, 1 -Saturated or unsaturated aliphatic thiols such as dodecanethiol, 1-tetradecanethiol, 1-hexadecanethiol, 1-octadecanethiol, cyclohexanethiol, allyl mercaptan, aromatics such as benzenethiol, benzyl mercaptan, 2-phenylethyl mercaptan Thiol is mentioned. A compound having a carboxyl group and a mercapto group in the molecule, such as 3-mercaptopropionic acid, can also be used.

  Examples of the compound having a hydroxy group in a reaction for producing an ether by a dehydration condensation reaction between a hydroxy group and a hydroxy group include the alcohols described above.

4). Reaction Conditions for Dehydration Condensation Reaction The dehydration condensation reaction (esterification, etherification, thioetherification, etc.) of the present invention can be carried out in the same manner under the following reaction conditions regardless of the type of reaction.
When two kinds of reaction substrates are used in the reaction, the substance amount ratio of both reaction substrates (for example, in the case of esterification reaction, the molar ratio of alcohol / carboxylic acid) is preferably in the range of 0.1 to 10, depending on the purpose. It is selected appropriately. From the viewpoint of reducing the unreacted reaction substrate remaining after the reaction, the substance amount ratio of both reaction substrates is more preferably in the range of 0.5 to 2.0, and most preferably 1.0.
The use amount (catalytic amount) of the surfactant type catalyst is preferably 0.1 to 100 mol%, more preferably 1 to 20 mol%, based on whichever of the substrates to be reacted is smaller. preferable. When the amount is less than 0.1 mol%, a preferable reaction rate cannot be obtained. When the amount is more than 100 mol%, the cost for the catalyst increases, which is not economically preferable.

There is no restriction | limiting in particular in reaction temperature, Although the temperature according to the objective can be set, the range of 20-120 degreeC is preferable, and the range of 30-90 degreeC is further more preferable. If the temperature is too low, the reaction rate is slow, and if it exceeds 120 ° C., the energy cost is increased, which is not preferable.
The reaction pressure is not particularly limited, and any conditions can be selected. However, from the viewpoint of energy cost, a range from normal pressure to 0.1 MPaG is preferable.
Also, the reaction time is not particularly limited, and the reaction time can be selected according to the purpose. The reaction time varies depending on the temperature, amount of catalyst, and amount of reaction substrate, but is preferably in the range of 10 minutes to 48 hours, more preferably in the range of 10 minutes to 24 hours, and most preferably in the range of 10 minutes to 12 hours. .

  The dehydration condensation reaction of the present invention is characterized in that it is carried out in water. The dehydration condensation reaction is presumed to proceed in micelles formed by the surfactant-type catalyst of the present invention and a hydrophobic reaction substrate. The amount of the surfactant-type catalyst used for water, which is a micelle dispersion medium, is preferably 0.001 to 0.5 mol per liter of water. Further, the concentration of the reaction substrate is preferably 0.05 to 10.0 mol / L.

  EXAMPLES Hereinafter, although the synthesis example of a catalyst, an Example, and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to the following example.

Synthesis Example 1: Synthesis of C26 four-branched alkylbenzene sulfonic acid
A THF solution of (2-butyloctyl) magnesium bromide (155 mmol) separately prepared in a tetrahydrofuran (THF) suspension (200 mL) of anhydrous cerium chloride (155 mmol, 38.2 g) at 0 ° C. under an argon atmosphere ( 150 mL) was added dropwise. The mixture was stirred at 0 ° C. for 2 hours, and then a solution of methyl phenylacetate (44.3 mmol, 6.65 g) in THF (60 mL) was added dropwise, and the mixture was stirred for 16 hours while maintaining 0 ° C. The reaction was stopped by adding a 10% aqueous acetic acid solution (200 mL), THF was distilled off under reduced pressure, and 2N hydrochloric acid was added to completely dissolve the insoluble matter. Thereafter, extraction was performed using diethyl ether, and the collected organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution and water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Purification by column chromatography (silica gel, chloroform: hexane = 1: 6 (volume ratio)) gave the desired tertiary alcohol (32.3 mmol, 14.8 g) in a yield of 73%.

  The synthesized tertiary alcohol (24.0 mmol, 11.0 g) and p-toluenesulfonic acid monohydrate (0.96 mmol, 0.18 g) were added to benzene (200 mL), followed by stirring under reflux for 15 hours. did. The reaction mixture was washed with a saturated aqueous solution of sodium bicarbonate and water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain an olefin mixture composed of three types of structural isomers. 10% Palladium carbon (0.99 g), THF (10 mL), and acetic acid (20 mL) were added to the obtained olefin mixture, and the mixture was stirred at room temperature for 4 days under a hydrogen pressure of 8 atm. After completion of the reaction, palladium carbon was removed by filtration, an excess amount of hexane was added to the filtrate, washed with a saturated aqueous sodium hydrogen carbonate solution and water, and dried over anhydrous sodium sulfate. By removing the highly polar component by column chromatography (silica gel, hexane), the target tetra-branched alkylbenzene (19.7 mmol, 8.72 g) was obtained in a yield of 82% from the previous reaction.

The tetra-branched alkylbenzene (4.00 mmol, 1.77 g) was dissolved in dichloromethane (50 mL), 60% fuming sulfuric acid (0.5 mL) was added dropwise at 0 ° C., and the mixture was stirred for 30 minutes. After the reaction was completed, a small amount of water was added to stop the reaction, and the aqueous layer and the organic layer were separated. A 3N aqueous sodium hydroxide solution was added to the organic layer, dichloromethane was distilled off under reduced pressure, and the precipitated solid was collected by filtration. The collected solid was dissolved again in dichloromethane, washed several times with 2N hydrochloric acid and water, and then cellulose powder was added to the organic layer and dried. After the cellulose powder was removed by filtration, the objective C26 four-branched alkylbenzene sulfonic acid was obtained almost quantitatively by concentration under reduced pressure. The structures of the synthesized intermediate and final product were all confirmed by measuring ¹ H-NMR and ¹³ C-NMR.

Synthesis Example 2: Synthesis of C18 four-branched alkylbenzene sulfonic acid
C18 four-branched alkylbenzene sulfonic acid was synthesized in the same manner by changing (2-butyloctyl) magnesium bromide in Synthesis Example 1 to (2-ethylhexyl) magnesium bromide.

Synthesis Example 3: Synthesis of C24 bibranched alkylbenzene sulfonic acid
Under an argon atmosphere, to a diethyl ether solution (80 mL) of n-dodecylmagnesium bromide (97.3 mmol), a diethyl ether solution (100 mL) of dodecanophenone (70.0 mmol, 18.2 g) was added dropwise at room temperature. Stir for 24 hours. A small amount of ice water was added to stop the reaction, and 2N hydrochloric acid was slowly added while cooling until the solution became transparent, followed by extraction with diethyl ether to separate the organic layer and the aqueous layer. The collected organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. Purification by column chromatography (silica gel, chloroform: hexane = 1: 4 (volume ratio)) gave the desired tertiary alcohol (59.5 mmol, 25.6 g) in a yield of 85%.

  The synthesized tertiary alcohol (24.0 mmol, 10.3 g) and p-toluenesulfonic acid monohydrate (0.96 mmol, 0.18 g) were added to toluene (200 mL), followed by stirring under reflux for 6 hours. did. The reaction mixture was washed with a saturated aqueous solution of sodium bicarbonate and water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain an olefin mixture composed of four types of structural isomers. 5% Palladium carbon (0.50 g) and ethanol (50 mL) were added to the obtained olefin mixture, and the mixture was stirred at room temperature for 24 hours in a hydrogen atmosphere. After completion of the reaction, palladium carbon was removed by filtration, and the highly polar component was removed by column chromatography (silica gel), whereby the desired bibranched alkylbenzene (16.8 mmol, 6.97 g) was obtained through the previous reaction. Obtained at 70%.

Bi-branched alkylbenzene (4.00 mmol, 1.66 g) was dissolved in dichloromethane (50 mL), 60% fuming sulfuric acid (0.5 mL) was added dropwise at 0 ° C., and the mixture was stirred for 30 min. After the reaction was completed, a small amount of water was added to stop the reaction, and the aqueous layer and the organic layer were separated. A 3N aqueous sodium hydroxide solution was added to the organic layer, dichloromethane was distilled off under reduced pressure, and the precipitated solid was collected by filtration. The collected solid was dissolved again in dichloromethane, washed several times with 2N hydrochloric acid and water, and then cellulose powder was added to the organic layer and dried. After the cellulose powder was removed by filtration, the target C24 bibranched alkylbenzene sulfonic acid was obtained almost quantitatively by concentration under reduced pressure. The structures of the synthesized intermediate and final product were all confirmed by measuring ¹ H-NMR and ¹³ C-NMR.

Synthesis Example 4: Synthesis of C18 bifurcated alkylbenzene sulfonic acid
C18 bibranched alkylbenzenesulfonic acid was synthesized in the same manner by changing n-dodecylmagnesium bromide and dodecanophenone in Synthesis Example 3 to n-octylmagnesium bromide and decanophenone, respectively.

Synthesis Example 5: Synthesis of C18 linear alkylbenzene sulfonic acid
n-Octadecylbenzene (3.74 mmol, 1.23 g) was dissolved in dichloromethane (50 mL), 60% fuming sulfuric acid (0.5 mL) was added dropwise at 0 ° C., and the mixture was stirred for 20 min. A small amount of water was added to stop the reaction, and dichloromethane was distilled off under reduced pressure. Then, a 3N sodium hydroxide aqueous solution was added to precipitate a solid. The precipitated solid was collected by filtration, washed with ice water, and then dried under reduced pressure to obtain sodium n-octadecylbenzenesulfonate (3.66 mmol, 1.58 g) in a yield of 98%.
The synthesized sodium n-octadecylbenzenesulfonate (1.01 mmol, 0.438 g) was added to 500 mL of water and heated to 90 ° C. to completely dissolve it. This aqueous solution was continuously passed through a glass column tube (inner diameter 2.5 cm, resin volume 54 cm ³ , equivalent to about 92 mmol in terms of sulfo group) filled with Amberlyst 15J WET (manufactured by Organo Corporation), which is a strongly acidic ion exchange resin. did. The target C18 linear alkylbenzene sulfonic acid was obtained by concentrating and drying the aqueous solution after passing through. By quantifying hydrogen ions in the product by neutralization titration, it was confirmed that the sodium form was almost completely converted to the acid form. In addition, the used ion exchange resin used what wash | cleaned thoroughly by flowing a lot of water beforehand.

Synthesis Example 6 Synthesis of C12 linear alkylbenzene sulfonic acid
C12 linear alkylbenzene sulfonic acid was synthesized in the same manner by changing n-octadecylbenzene in Synthesis Example 5 to n-dodecylbenzene.

Example 1: Esterification reaction using C26 four-branched alkylbenzene sulfonic acid catalyst
Lauric acid (0.25 mmol, 0.050 g), 3-phenyl-1-propanol (0.25 mmol, 0.034 g), C26 four-branched alkylbenzenesulfonic acid prepared in Synthesis Example 1 against water (1.5 mL) (0.025 mmol, 0.013 g) was added, and the mixture was stirred at 40 ° C. for an arbitrary time. When stirring was started, the reaction solution quickly formed a white cloudy emulsion. After completion of the reaction, the reaction was stopped by adding a saturated aqueous sodium hydrogen carbonate solution, and the organic component was extracted with ethyl acetate, washed with brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. ¹ H-NMR (CDCl ₃ ) was measured, and the yield was determined from the integral ratio of the produced ester and unreacted alcohol. The relationship between reaction time and ester yield is shown in Table 1 and FIG.

Example 2: Esterification reaction using C24 bi-branched alkylbenzene sulfonic acid catalyst Example 1 except that C24 bi-branched alkyl benzene sulfonic acid (0.025 mmol, 0.012 g) prepared in Synthesis Example 3 was used as a catalyst. The same was done. The relationship between reaction time and yield is shown in Table 1 and FIG.

Example 3 Esterification Reaction Using C18 Four-Branched Alkylbenzenesulfonic Acid Catalyst Example 1 except that C18 four-branched alkylbenzenesulfonic acid (0.025 mmol, 0.010 g) was used as the catalyst produced in Synthesis Example 2. The same was done. The relationship between reaction time and yield is shown in Table 1 and FIG.

Example 4: Esterification reaction using C18 bibranched alkylbenzene sulfonic acid catalyst Example 1 except that C18 bibranched alkyl benzene sulfonic acid (0.025 mmol, 0.010 g) prepared in Synthesis Example 4 was used as a catalyst. The same was done. The relationship between reaction time and yield is shown in Table 1 and FIG.

Comparative Example 1: Esterification reaction using a C18 linear alkylbenzene sulfonic acid catalyst Example 1 except that the C18 linear alkylbenzene sulfonic acid (0.025 mmol, 0.010 g) prepared in Synthesis Example 5 was used as a catalyst. The same was done. The relationship between reaction time and yield is shown in Table 1 and FIG.

Comparative Example 2: Esterification reaction using a C12 linear alkylbenzene sulfonic acid catalyst Example 1 except that the C12 linear alkylbenzene sulfonic acid (0.025 mmol, 0.0082 g) prepared in Synthesis Example 6 was used as a catalyst. The same was done. The relationship between reaction time and yield is shown in Table 1 and FIG.

  Regarding Examples 1 to 4 and Comparative Examples 1 and 2, Table 1 and FIG. 1 show the relationship between the reaction time and the yield of the ester which is the product of the dehydration condensation reaction. As can be seen from these, C26 four-branched, C24 two-branched, C18 four-branched, and C18 two-branched catalysts that have newly introduced long-chain branched alkyl structures are the conventional catalysts C18 linear and C12 straight. Compared with the chain type catalyst, it showed high catalytic activity. In particular, C26 four-branch type, C24 two-branch type and C18 two-branch type catalysts show a significant improvement in yield, and have a short reaction time (about 0 to 10 hours) with little influence of equilibrium yield. (Fig. 1). On the other hand, when the C18 linear type catalyst and the C12 linear type catalyst were compared with each other, they showed almost the same catalytic activity, and it was found that a simple increase in the number of alkyl carbons hardly affected the reaction. That is, it is shown that introduction of an appropriate branched structure is very important for improving catalytic activity.

Examples 5 to 10: Esterification reaction of various carboxylic acids and various alcohols using a C26 four-branched alkylbenzene sulfonic acid catalyst
Various esterification reactions were carried out using carboxylic acid and alcohol shown in Table 2 as reaction substrates. To water (1.5 mL), carboxylic acid (0.25 mmol), alcohol (0.50 mmol), and C26 four-branched alkylbenzene sulfonic acid (0.0125 mmol, 0.0065 g) prepared in Synthesis Example 1 were added, and 40 ° C. For 24 hours. When stirring was started, the reaction solution quickly formed a white cloudy emulsion. After completion of the reaction, the reaction was stopped by adding a saturated aqueous sodium hydrogen carbonate solution, and the organic component was extracted with ethyl acetate, washed with brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The desired ester was isolated by purification by preparative thin layer chromatography, and the structure was confirmed by measuring ¹ H-NMR (CDCl ₃ ). Table 2 shows the ester yield of each reaction. The reaction proceeded quickly and the desired ester could be obtained in high yield. In addition, since the production | generation speed | rate of the symmetrical ether of primary alcohol which is one reaction substrate is very slow compared with esterification, since the ester is more thermodynamically stable, ether was hardly produced | generated. .

Examples 11-14: Synthesis of ethers using C26 four-branched alkylbenzene sulfonic acid catalyst

Examples 11-12
A symmetric ether was synthesized using the alcohol shown in Table 3 as a reaction substrate. Alcohol (0.50 mmol) and C26 tetrabranched alkylbenzene sulfonic acid (0.0125 mmol, 0.0065 g) produced in Synthesis Example 1 were added to water (1.5 mL), and each was carried out at the temperatures shown in Table 3 for 24 hours. Stir. When stirring was started, the reaction solution quickly formed a white cloudy emulsion. After completion of the reaction, the reaction was stopped by adding a saturated aqueous sodium hydrogen carbonate solution, and the organic component was extracted with ethyl acetate, washed with brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. By purifying by preparative thin layer chromatography, the target ether was isolated and ¹ H-NMR (CDCl ₃ ) was measured to confirm the structure. Table 3 shows the yield of ether.

Examples 13-14
The reaction was carried out in the same manner as in Examples 11 to 12 except that two kinds of alcohols shown in Table 3 were used, and the results shown in Table 3 were obtained.
In Examples 13 and 14, symmetrical ethers of 1-dodecanol, which are primary alcohols, are extremely slow in production rate and hardly formed. Also, since the asymmetric ether with 1-dodecanol is thermodynamically more stable than the symmetrical ether between diphenylcarbinol and the symmetrical ether between 2-phenyl-2-propanol, the asymmetric ether is the main product. Become. The reaction proceeded rapidly and the desired ether could be obtained in high yield.

Examples 15 to 18: Thioetherification reaction using C26 four-branched alkylbenzene sulfonic acid catalyst
Various thioetherification reactions were performed using thiols and alcohols shown in Table 4 as reaction substrates. To water (1.5 mL), thiol (0.25 mmol), alcohol (0.50 mmol or 0.25 mmol), and C26 four-branched alkylbenzenesulfonic acid (0.0125 mmol, 0.0065 g) prepared in Synthesis Example 1 were added. , Each was stirred at the temperature described in Table 4 for 24 hours. When stirring was started, the reaction solution quickly formed a white cloudy emulsion. After completion of the reaction, the reaction was stopped by adding a saturated aqueous sodium hydrogen carbonate solution, and the organic component was extracted with ethyl acetate, washed with brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The target thioether was isolated by purification by preparative thin layer chromatography, and the structure was confirmed by measuring ¹ H-NMR (CDCl ₃ ). Table 4 shows the yield of thioether for each reaction. Since thioether is thermodynamically more stable than ether, thioether is predominantly produced in an equilibrium state. The reaction proceeded quickly and the desired thioether was obtained in high yield.

Claims (8)

In a method for producing an organic compound by dehydration condensation in water between reaction substrates in which at least one of the reaction substrates is a hydrophobic compound, the general formula (I)
(In the formula, R ¹ and R ² represent a linear or branched alkyl group having 6 to 30 carbon atoms, R ¹ and R ² may be the same or different, and n is 0, or 1 to 3; A method for producing an organic compound, which comprises using a surfactant-type catalyst represented by the following formula: Manufacturing method of R ¹ and R ² in general formula (I) is an organic compound according to claim 1, each independently represent a linear or branched alkyl group having 8 to 20 carbon atoms. The organic group according to claim ^1, wherein R ¹ and R ^{2 in} the general formula (I) each independently represent a linear alkyl group having 8 to 14 carbon atoms or an alkyl group having 10 to 16 carbon atoms having one branch. Compound production method.   N in general formula (I) is 0 or 1, The manufacturing method of the organic compound in any one of Claims 1-3.   All the reaction substrates are hydrophobic compounds, The manufacturing method of the organic compound in any one of Claims 1-4.   The method for producing an organic compound according to any one of claims 1 to 5, wherein the dehydration condensation reaction is any one of an esterification reaction, an etherification reaction, and a thioetherification reaction.   The method for producing an organic compound according to claim 6, wherein the dehydration condensation reaction is an esterification reaction.   The method for producing an organic compound according to claim 7, wherein the dehydration condensation reaction is an esterification reaction between an alcohol having 4 to 30 carbon atoms and a carboxylic acid having 4 to 30 carbon atoms.