KR19980067531A - Method for preparing N-alkyl-β-hydroxy ethyl sulfon aniline derivative - Google Patents

Abstract

The present invention relates to a process for the preparation of N-alkyl-β-hydroxy ethyl sulfone aniline derivatives.

The present invention relates to the use of aldehydes or ketones and β- (hydroxyethyl sulfone) nitrobenzene or β- (hydroxyethyl sulfone) aniline in co-catalysts in combination with a catalyst belonging to the Group VIII precious metals of the periodic table in an alcohol or ketone solvent. And N-alkyl-β-hydroxy ethyl sulfone aniline derivatives in the preparation of N-alkyl-β-hydroxy ethyl sulfone aniline derivatives by maximizing the selectivity and activity of the catalyst to shorten the reaction time. It has the effect of improving the purity.

Description

Method for preparing N-alkyl-β-hydroxy ethyl sulfon aniline derivative

The present invention relates to a process for the preparation of N-alkyl-β-hydroxy ethyl sulfone aniline derivatives used as raw materials for reactive preparation dyes.

Conventional methods for producing N-alkyl-β-hydroxy ethyl sulfone aniline derivatives include aldehydes or ketones and β- (hydroxy ethyl sulfone) nitrobenzene or β- (hydroxy ethyl sulfone) aniline in an alcohol solvent. Hydrogenated alkylation using a catalyst belonging to group VIII of the noble metal is the most common method, but when reacting according to this method, it takes about 3 to 10 hours to complete the reaction. There was a problem of low purity.

The present invention has been devised to solve the above-mentioned conventional problems, and maximizes the selectivity and activity of the catalyst to shorten the reaction time and improve the purity of the prepared N-alkyl-β-hydroxy ethyl sulfone aniline derivatives. It is an object to provide a process for the preparation of N-alkyl-β-hydroxy ethyl sulfone aniline derivatives.

The method for producing an N-alkyl-β-hydroxy ethyl sulfone aniline derivative of the present invention for achieving this object is aldehyde or ketones and β- (hydroxy ethyl sulfone) nitrobenzene or β- (hydroxy ethyl sulfone) aniline Is reacted under constant temperature and pressure using a cocatalyst with a catalyst belonging to the noble metal group VIII of the periodic table in an alcohol or ketone solvent.

The present invention relates to the use of aldehydes or ketones and β- (hydroxyethyl sulfone) nitrobenzene or β- (hydroxyethyl sulfone) aniline in co-catalysts in combination with a catalyst belonging to the Group VIII precious metals of the periodic table in an alcohol or ketone solvent. And reaction under constant pressure to prepare N-alkyl-β-hydroxy ethyl sulfone aniline derivatives.

Β- (hydroxyethyl sulfone) nitro benzene used in the present invention is a compound having the following structural formula,

β- (hydroxy ethyl sulfone) aniline is a compound having the structure

In addition, aldehyde and ketone refer to a compound having the following structural formula.

(Wherein R ₁ , R ₂ is an alkyl group having the formula of H or C _n H _{2n + 1} )

As for the reaction ratio of (beta)-(hydroxy ethyl sulfone) nitrobenzene or (beta)-(hydroxy ethyl sulfone) aniline, and an aldehyde or a ketone, as a reaction ratio, 1: 1-1.5 are preferable in molar ratio.

For example, an element belonging to the Group VIII of the periodic table such as nickel, palladium, platinum and the like can be used as a catalyst, and palladium deposited on a carrier, platinum deposited on a carrier, activated nickel, and the like are preferable. The element belonging to the noble metal group VIII used as a catalyst is preferably 1.5 to 3% by weight of β- (hydroxy ethyl sulfone) nitrobenzene or β- (hydroxy ethyl sulfone) aniline.

Activated carbon or phosphoric acid is used as a promoter and it is preferable to use 0.001 to 3% of the weight of β- (hydroxy ethyl sulfone) nitrobenzene or β- (hydroxy ethyl sulfone) aniline.

The constant temperature and the constant pressure are preferably in the temperature range of 50 to 160 ° C. and the pressure range of 5 to 50 kg / cm ² of hydrogen pressure.

In the present invention, ketones and β- (hydroxy ethyl sulfone) nitrobenzene or β- (hydroxy ethyl sulfone) aniline are used as a solvent without using an alcohol solvent as reactants, and precious metals of the periodic table such as nickel, palladium, and platinum are used. When the N-alkyl-β-hydroxyethyl sulfone aniline derivative is prepared by reacting a catalyst belonging to the group with a cocatalyst such as activated carbon or phosphoric acid at a constant temperature and a constant pressure, the reaction rate and the purity of the product may be further improved. Can be.

Hereinafter, the present invention will be described in detail with reference to the following examples, which are only examples of the present invention, but the present invention is not limited thereto.

Example 1

70 g of 3-β- (hydroxy ethyl sulfone) aniline, 200 g of methanol, 1.56 g of 5% Pd / C (palladium catalyst on carbon), 0.03 to 0.05 g of phosphoric acid as a promoter, and 17.6 g of acetaldehyde were added to the reactor Was sealed and air was replaced with nitrogen.

The reduction alkylation reaction was performed for 40 minutes at the temperature of 80-95 degreeC, and the pressure of 30-40 kg / cm <^2> . After filtration of the catalyst, the solvent was distilled off under reduced pressure to obtain 3-β- (hydroxy ethyl sulfone) -N-ethyl aniline and the conversion was 100%.

HPLC (high pressure liquid chromatography) analysis showed that the obtained 3-β- (hydroxy ethyl sulfone) -N-ethyl aniline had a purity of 91% or more.

Example 2

70 g of 3-β- (hydroxy ethyl sulfone) nitrobenzene, 200 g of methanol, 1.56 g of 5% Pd / C (palladium catalyst on carbon), 1.56 g of activated carbon as a promoter, and 17.4 g of acetaldehyde were added to the reactor, and then the reactor was It was sealed and air was replaced with nitrogen.

The initial hydrogen pressure is 5 ~ 15 kg / cm ² , the temperature is 80 ℃ or less, the reaction proceeds for 30 minutes, and the pressure is raised to 30 ~ 40 kg / cm ² and the temperature is 80 ~ 95 ℃ for 40 minutes. Proceeded. After filtration of the catalyst, the solvent was distilled off under reduced pressure to obtain 3-β- (hydroxy ethyl sulfone) -N-ethyl aniline. The total reaction time was 70 minutes and the conversion was 100%.

HPLC (high pressure liquid chromatography) analysis showed that the obtained 3-β- (hydroxy ethyl sulfone) -N-ethyl aniline had a purity of 91% or more.

Example 3

70 g of 3-β- (hydroxy ethyl sulfone) nitrobenzene, 200 g of methanol, 1.56 g of 5% Pd / C (palladium catalyst on carbon), 0.03 to 0.05 g of phosphoric acid as a promoter, and 17.4 g of acetaldehyde were added to the reactor. The reactor was sealed and air was replaced with nitrogen.

The initial hydrogen pressure is 5 ~ 15 kg / cm ² , the temperature is 80 ℃ or less, the reaction proceeds for 20 minutes, and the pressure is raised to 30 ~ 40 kg / cm ² and the temperature is 80 ~ 95 ℃ for 50 minutes. Proceeded. After filtration of the catalyst, the solvent was distilled off under reduced pressure to obtain 3-β- (hydroxy ethyl sulfone) -N-ethyl aniline and the conversion was 100%.

As a result of HPLC (high pressure liquid chromatography) analysis, the obtained 3-β- (hydroxy ethyl sulfone) -N-ethyl aniline had a purity of 90% or more.

Example 4

70 g of 3-β- (hydroxy ethyl sulfone) aniline, 200 g of methanol, 1.56 g of 5% Pd / C (palladium catalyst on carbon), 1.56 g of activated carbon as a promoter, and 17.4 g of acetaldehyde were placed in the reactor, and the reactor was sealed. And air was replaced with nitrogen.

The reduction alkylation reaction was performed for 40 minutes at the temperature of 80-95 degreeC, and the pressure of 30-40 kg / cm <^2> . After filtration of the catalyst, the solvent was distilled off under reduced pressure to obtain 3-β- (hydroxy ethyl sulfone) -N-ethyl aniline and the conversion was 100%.

HPLC (high pressure liquid chromatography) analysis showed that the obtained 3-β- (hydroxy ethyl sulfone) -N-ethyl aniline had a purity of 91% or more.

Example 5

70 g of 3-β- (hydroxy ethyl sulfone) nitrobenzene, 200 g of acetone, 1.56 g of 3% Pt / C (platinum catalyst on carbon), 0.03 to 0.05 g of phosphoric acid as a promoter, the reactor was sealed and air Was replaced with nitrogen.

The initial hydrogen pressure was 5 ~ 15 kg / cm ² , the temperature was lowered to 80 ° C. for 30 minutes, the pressure was raised to 30-40 kg / cm ² , and the temperature was raised to 150 ° C. for 60 minutes. . After filtration of the catalyst, the solvent was distilled off under reduced pressure to obtain 3-β- (hydroxy ethyl sulfone) -N-isopropyl benzene. The total reaction time was 90 minutes and the conversion was 100%.

HPLC (high pressure liquid chromatography) analysis showed that the obtained 3-β- (hydroxy ethyl sulfone) -N-isopropyl benzene had a purity of 95% or more.

Example 6

70 g of 3-β- (hydroxy ethyl sulfone) nitrobenzene, 200 g of acetone, 1.56 g of 3% Pt / C (platinum catalyst on carbon), 1.56 g of activated carbon as a promoter were placed in the reactor, and the reactor was sealed and air was Substituted by

The initial hydrogen pressure was 5 ~ 15 kg / cm ² , the temperature was lowered to 80 ° C. for 30 minutes, and the pressure was raised to 30-40 kg / cm ² and the temperature was raised to 150 ° C. for 40 minutes. . After filtration of the catalyst, the solvent was distilled off under reduced pressure to obtain 3-β- (hydroxy ethyl sulfone) -N-isopropyl benzene. The total reaction time was 80 minutes and the conversion was 100%.

HPLC (high pressure liquid chromatography) analysis showed that the obtained 3-β- (hydroxy ethyl sulfone) -N-isopropyl benzene had a purity of 95% or more.

The following comparative experiments were carried out to compare the time required and the yield of the conventional method using no cocatalyst in the preparation of N-alkyl-β-hydroxyethyl sulfone aniline derivatives and the preparation method of the present invention using the cocatalyst. It was.

Comparative Example 1

70 g of 3-β- (hydroxy ethyl sulfone) nitrobenzene, 200 g of methanol, 1.56 g of 5% Pd / C (carbon-based palladium catalyst) and 17.4 g of acetaldehyde were placed in the reactor, and the reactor was sealed and air was replaced with nitrogen. It was.

The initial hydrogen pressure is 5 ~ 15 kg / cm ² , the temperature is 80 ℃ or less, and the reaction proceeds for 30 minutes, and then the hydrogen pressure is raised to 30 ~ 40 kg / cm ² and the temperature is 85-95 ℃ and reduced for 2 hours 30 minutes. The alkylation reaction proceeded. After filtration of the catalyst, the solvent was distilled under reduced pressure to obtain 3-β- (hydroxy ethyl sulfone) -N-ethyl aniline, and the total reaction time was 3 hours and the conversion was 100%. The reduction alkylation reaction was performed for 40 minutes at the temperature of 80-95 degreeC, and the pressure of 30-40 kg / cm <^2> . After filtration of the catalyst, the solvent was distilled off under reduced pressure to obtain 3-β- (hydroxy ethyl sulfone) -N-ethyl aniline and the conversion was 100%.

HPLC (high pressure liquid chromatography) analysis showed that the obtained 3-β- (hydroxy ethyl sulfone) -N-ethyl aniline had a purity of 87% or more.

Comparative Example 2

70 g of 3-β- (hydroxy ethyl sulfone) nitrobenzene, 200 g of methanol, 1.56 g of 3% Pt / C (platinum catalyst on carbon) and 26.7 g of acetone were placed in the reactor, and the reactor was sealed and air was replaced with nitrogen. .

The initial hydrogen pressure is 5 ~ 15 kg / cm ² , the temperature is 80 ℃ or less, and the reaction proceeds for 30 minutes, and then the hydrogen pressure is raised to 30 ~ 40 kg / cm ² and the temperature is 150 ℃ for 4 hours 30 minutes Proceeded. After filtration of the catalyst, the solvent was distilled off under reduced pressure to obtain 3-β- (hydroxy ethyl sulfone) -N-isopropyl aniline. The total reaction time was 5 hours and the conversion was 98%.

As a result of HPLC (high pressure liquid chromatography) analysis, the purity of the obtained 3-β- (hydroxy ethyl sulfone) -N-isopropyl aniline was 90-93%.

As described in detail above, the present invention provides crude aldehyde or ketones and β- (hydroxy ethyl sulfone) nitrobenzene or β- (hydroxy ethyl sulfone) aniline together with a catalyst belonging to the Group VIII of the precious metal of the periodic table in an alcohol or ketone solvent. In the preparation of N-alkyl-β-hydroxy ethyl sulfon aniline derivatives by reacting at a constant temperature and a constant pressure using a catalyst, the reaction time can be significantly shortened and the purity and yield of the product can be improved.

Claims (7)

One compound selected from the group consisting of compounds of formulas (I) and (II) One compound selected from the group consisting of alcohols or ketones of formula (III) (Wherein R ₁ , R ₂ is an alkyl group having the formula of H or C _n H _{2n + 1} ) In a solvent selected from the group consisting of alcohols or ketones, a cocatalyst is added to the noble metal catalyst of the Group VIII periodic table, followed by a reduction alkylation reaction at a constant pressure and at a constant temperature to form N-alkyl-β-hydroxy of formula (IV) Process for preparing ethyl sulfon aniline derivatives. (Wherein R ₁ , R ₂ is an alkyl group having the formula of H or C _n H _{2n + 1} ) The method for preparing an N-alkyl-β-hydroxy ethyl sulfone aniline derivative according to claim 1, wherein only ketones are used as a solvent and a reactant instead of a separate solvent. 3. The method of claim 1, wherein the promoter is selected from the group consisting of activated carbon or phosphoric acid. 4. 3. The N-alkyl-β-hydride according to claim 1 or 2, wherein the precious metal catalyst of Group VIII of the periodic table is selected from the group consisting of platinum deposited on a carrier, palladium deposited on a carrier and activated nickel. Process for the preparation of oxyethyl sulfon aniline derivatives. The use ratio of one compound according to claim 1 or 2, wherein the compound selected from the group consisting of the compounds of formulas (I) and (II) and one compound selected from the group consisting of alcohols or ketones of the formula (III) The method for producing an N-alkyl-β-hydroxy ethyl sulfon aniline derivative, characterized in that the molar ratio of 1: 1 to 1.5. The N-alkyl-β-hydroxyethyl sulfone according to claim 1 or 2, wherein the noble metal catalyst of Group VIII of the periodic table uses 1.5 to 3.0% of the weight of the compound of formula (I). Process for the preparation of aniline derivatives. The N-alkyl-β-hydroxyethyl sulfone aniline derivative of claim 1 or 2, wherein the constant pressure is 5 to 50 kg / cm ² of hydrogen pressure, and the predetermined temperature is 50 to 160 ° C. Manufacturing method.