WO2016072941A1

WO2016072941A1 - Diethanolamine derivatives and a preparation method thereof

Info

Publication number: WO2016072941A1
Application number: PCT/TH2015/000076
Authority: WO
Inventors: Papapida PORNSURIYASAK; Anupat POTISATITYUENYONG
Original assignee: PTT Global Chemical PCL
Current assignee: PTT Global Chemical PCL
Priority date: 2014-11-05
Filing date: 2015-11-05
Publication date: 2016-05-12
Anticipated expiration: 2017-05-05

Abstract

This invention relates to a method for preparing diethanolamine derivatives having the structure (I): Formula (I); wherein Formula (II); R₁ represents structure (II) R₂ represents hydrogen or structure (II); X represents hydrogen, alkali or alkaline earth metal; by reacting diethanolamine with maleic anhydride, butenedioic acid or butenedioic acid salts in the presence of alkali or alkaline earth metal hydroxide.

Description

DIETHANOLAMINE DERIVATIVES AND A PREPARATION METHOD THEREOF

FIELD OF THE INVENTION

The present invention relates to a chemical field of diethanolamine derivatives and a method for preparing said diethanolamine derivatives. BACKGROUND OF THE INVENTION

At present, chelating agent product in the market requires degradable product to reduce effects to the environment but still providing effectiveness in metal chelating as same as or comparable to the products widely used in present market, for example, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA) which are non- degradable and highly toxic. Examples of degradable chelating agents produced in industrial scales are methylglycinediacetic acid (MGDA), glutamic acid Ν,Ν-diacetic acid (GLDA), iminodisuccinic acid (IDS), and dihydroxyethylglycine (DHEG). Problemy Khimii Kompleksonov (1985), pages 108-1 15 disclosed a preparation method for aminopolycarbonate chelating agent comprising the steps of esterification of aspartic acid in methanol and hydrochloric acid solution to obtain methyl aspartate, following by ethoxylation and hydrolysis reactions of methyl ester, to obtain dihydroxyethyl aspartate as a final product. It can be seen that this method is complicated with many steps, thus not suitable for industrial application. European Patent No. EP1086944B1 disclosed a method for synthesizing L-aspartic acid derivatives having similar structure to dihydroxyethyl aspartate. The method was performed by the ethoxylation reaction of L-aspartic acid following by addition reaction of maleic anhydride to obtain L-aspartic acid derivative. Moreover, it was found that diethanolamine derivative having substitution on nitrogen and oxygen position or aminocarboxylate group with free hydroxyl group shows an increase of biodegradability. However, the ethoxylation according to the above-mentioned Problemy Khimii Kompleksonov and European Patent No. EP 1086944B1 required ethylene oxide which is dangerous substance, high reactivity, and high flammable, therefore, careful handling is needed with this kind of substance.

U.S. Patent No. US6504054B1 disclosed a synthesis of aspartic acid derivative using L-aspartic acid ethoxylate or diethanolamine as a precursor. Then, addition reaction using lanthanum oxide as a catalyst was performed. It can be seen that in U.S. Patent No. US6590120B1 , addition reaction using lanthanide metal as a catalyst gave addition ofmaleate group on both nitrogen and oxygen positions of diethanolamine. This patent document also described the preparation method of amine compound by reacting alkali metal or salts of alkaline earth metal of maleic acid with diethanolamine having substituted group on nitrogen position using lanthanide metal or alkaline earth metal as a catalyst. However, using transition metal group as a catalyst causes high cost and need a purification step to remove the catalyst. Moreover, substitution reaction on three positions of diethanolamine cannot be controlled to be only on nitrogen position.

Japanese Patent No. JPH08208569 disclosed a method for synthesizing diethanolamine derivative by reacting diethanolamine with maleic acid or salts of maleic acid using co-catalyst of sodium hydroxide and calcium hydroxide. The product obtained by substitution reaction on two positions of diethanolamine, one on nitrogen and one on oxygen. However, this method needs a separation step of catalysts which makes the method more complicated.

Therefore, the present invention aims to prepare diethanolamine derivatives with high water solubility, high chelating activity, and biodegradability using less complex preparation method with low cost and reducing the use of toxic substances.

SUMMARY OF THE INVETION

This invention relates to a method for preparing diethanolamine derivatives having the structure (I):

Ri

I

HO-" -- N--_ -o^ ^R2 . wherein

_/co₂x

— CH^

Ri represents structure (II) ^C°^2X (II);

R₂ represents hydrogen or structure (II);

X represents hydrogen, alkali or alkaline earth metal;

by reacting diethanolamine with maleic anhydride, butenedioic acid or butenedioic acid salts in the presence of alkali or alkaline earth metal hydroxide. BRIEF DESCRIPTION OF THE DRAWING

Figure 1 shows a proton-nuclear magnetic resonance spectrum of dihydroxyethyl aspartate measured at 400 MHz by dissolving dihydroxyethyl aspartate in deuterium oxide (D₂0), Chemical shift results are 2.40-2.50 (dd, I H, OH_a), 2.54-2.61 (dd, I H, OH_b), 2.75-2.92 (m, 4Η, N-CH₂ x2), 3.52-3.86 (m, 7Η, 0-CH₂ x2, N-CH, N-CH-CH₂) ppm.

DETAILED DESCRIPTION OF THE INVENTION

Definition

Technical terms or scientific terms used herein, have definitions as understood by those having an ordinary skill in the art, unless stated otherwise.

Equipment, apparatus, methods, or chemicals mentioned here means equipment, apparatus, methods or chemicals commonly operated or used by those skilled in the art, unless explicitly stated otherwise that they are equipment, apparatus, methods, or chemicals specifically used in this invention.

The use of the singular or plural nouns with the term "comprising" in the claims or in the specification refers to "one" and also "one or more", "at least one", and "one or more than one".

Throughout this application, the term "about" is used to indicate that any value presented herein may potentially vary or deviate. Such variation or deviation may result from errors of apparatus, methods used in calculation or from individual operator implementing apparatus or methods. These include variations or deviations from changing of reaction conditions from uncontrollable factors such as humidity or temperature.

"Chelating agent" refers to organic substances that are able to bind with positive charge elements such as iron, zinc, copper, cobalt, manganese. Chelating agent will surround cation or positive charge of metal elements to be complex compound with metal bound in its molecule, so other anion cannot react. This reaction is called chelation.

"Degradable chelating agent" means biodegradable chelating agent such as chelating agent which can be degraded by heat, sunlight, or microorganism.

"Alkali or alkaline earth metal " means elements in group 1 or 2 of periodic table. Group 1 elements or alkali metals are lithium, sodium, potassium, rubidium, cesium, francium, and group 2 elements or alkaline earth metals are beryllium, magnesium, calcium, strontium, barium, radium.

Hereafter, invention embodiments are shown without any purpose to limit any scope of the invention.

The present invention relates to a method for preparing diethanolamine derivatives having the structure (I):

Ri

I

HO--~ N-~__^~-~-,₀,_^R₂ wherein

— CH

Ri represents structure (II) ^C°^2X (II);

R₂ represents hydrogen or structure (II);

X represents hydrogen, alkali or alkaline earth metal;

by reacting diethanolamine with maleic anhydride, butenedioic acid or butenedioic acid salts in the presence of alkali or alkaline earth metal hydroxide.

Preferable, the diethanolamine derivative has structure (III):

wherein X represents hydrogen, alkali or alkaline earth metal.

Most preferable, the diethanolamine derivative is dihydroxyethyl aspartate.

The method for preparing diethanolamine derivative, which is dihydroxyethyl aspartate may be shown as the following.

In said method, butenedioic acid or butenedioic acid salts are bonded to nitrogen position of diethanolamine.

The binding of butenedioic acid or butenedioic acid salts on nitrogen position of diethanolamine is carried out via addition reaction.

Alkali or alkaline earth metal hydroxide present in the method according to this invention may be alkali or alkaline earth metal hydroxide that already exists in the system or by addition.

Alkali or alkaline earth metal hydroxide may be added in either solid or liquid phase, depending on system condition and compatibility of alkali or alkaline earth metal hydroxide in such system.

Alkali or alkaline earth metal hydroxide may act as a reactant or catalyst. For example, being the reactant during the ring opening step, or being the catalyst during the addition reaction step.

Preferable, alkali or alkaline earth metal hydroxide is sodium hydroxide.

Preferable, alkali or alkaline earth metal hydroxide is used in an amount of 0.2 to 0.8 mole equivalent, more preferable in the amount of 0.3 to 0.5 mole equivalent.

Preferable, temperature used in the method for preparing diethanolarnine derivative is in a range of 80 to 120 °C, more preferable in the range of 1 10 to 120 °C.

In one embodiment, pH may be adjusted to be lower than 7 by adding organic acid. The followings are examples of the preparation of diethanolamine derivatives according to this invention without any intention to limit the scope of the invention.

Example 1

8.2 g (51 mmole) of disodium maleate was dissolved in 10 mL of water. Then, 5.36 g (51 mmole) of diethanolamine was added, following by 0.61 g (15.4 mmole or 0.3 mole equivalent) of sodium hydroxide. The reaction was carried out at room temperature for 48 hours. The compound obtained from the prior steps was evaporated under vacuum and crystallized in 200 mL of mixed organic solvents of methanol and ethyl acetate in a ratio of 1 :1. The obtained solid product was separated and dried under vacuum before analyzed using proton-nuclear magnetic resonance spectroscopy. Dihydroxyethyl aspartate was not found. Example 2

8.20 g (51 mmole) of disodium maleate was dissolved in 10 mL water. Then, 5.36 g (51 mmole) of diethanolamine was added, following by 0.20 g (5.1 mmole or 0.1 mole equivalent) of sodium hydroxide. The reaction was carried out at 1 10 °C for 24 hours. The compound obtained from the prior steps was evaporated under vacuum and crystallized in 200 mL of mixed organic solvents of methanol and ethyl acetate in a ratio of 1 :1. The obtained solid product was separated and dried under vacuum before analyzed using proton-nuclear magnetic resonance spectroscopy. Dihydroxyethyl aspartate was not found.

Example 3

8.20 g (51 mmole) of disodium maleate was dissolved in 10 mL of water. Then, 5.36 g

(51 mmole) of diethanolamine was added, following by 0.61 g (15.4 mmole or 0.3 mole equivalent) of sodium hydroxide. The reaction was carried out at 110 °C for 15 hours. The compound obtained from the prior steps was evaporated under vacuum and crystallized in 200 mL mixed organic solvents of methanol and ethyl acetate in a ratio of 1 :1. The obtained solid product was separated and dried under vacuum before analyzed using proton-nuclear magnetic resonance spectroscopy. Dihydroxyethyl aspartate yield was 77 %.

Example 4

5 g (51 mmole) of maleic anhydride was dissolved in 10 mL of water. Then, 4.08 g (102 mmole) of sodium hydroxide was prepared in 5 mL of water. Prepared sodium hydroxide solution was dropped into prepared maleic anhydride solution at a rate of 1 mL/min. This exothermic reaction increased the reaction temperature to 80 °C rapidly. After finishing adding base solution, the temperature reaction decreased to 30 °C within 15 minutes, then stirred the reaction mixture at 30 °C for at least 1 hour, following by adding 5.36 g (51 mmole) of diethanolamine and 0.20 g (5.1 mmole or 0.1 mole equivalent) sodium hydroxide. The reaction mixture was then refluxed at 80 °C for 24 hours. The compound obtained from the prior step was evaporated under vacuum and crystallized in 200 mL of mixed organic solvents of methanol and ethyl acetate in a ratio of 1 : 1. The obtained solid product was separated and dried under vacuum before analyzed using proton-nuclear magnetic resonance spectroscopy. Dihydroxyethyl aspartate was not found. Example 5

5 g (51 mmole) of maleic anhydride was dissolved in 10 mL of water. Then, 4.08 g (102 mmole) of sodium hydroxide was prepared in 5 mL of water. Prepared sodium hydroxide solution was dropped into prepared maleic anhydride solution at a rate of 1 mL/min. This exothermic reaction increased the reaction temperature to 80 °C rapidly. After finishing adding base solution the temperature reaction decreased to 30 °C within 15 minutes, then stirred the reaction mixture at 30 °C for at least 1 hour, following by adding 5.36 g (51 mmole) of diethanolamine and 0.61 g (15.4 mmole or 0.3 mole equivalent) of sodium hydroxide. The reaction mixture was refluxed at 80 °C for 24 hours. The compound obtained from the prior steps was evaporated under vacuum and crystallized in 200 mL of mixed organic solvents of methanol and ethyl acetate (ratio of 1 : 1) The solid product was separated and dried under vacuum before analyzed using proton-nuclear magnetic resonance spectroscopy. Dihydroxyethyl aspartate yield was 38 %.

Example 6

5 g (51 mmole) of maleic anhydride was dissolved in 10 mL of water. Then, 4.08 g

(102 mmole) of sodium hydroxide was prepared in 5 mL of water. Prepared sodium hydroxide solution was dropped into prepared maleic anhydride solution at a rate of 1 mL/min. This exothermic reaction increased the reaction temperature to 80 °C rapidly. After finishing adding base solution, the temperature reaction decreased 30 °C within 15 minutes, then stirred the reaction mixture at 30 °C for at least 1 hour, following by adding 5.36 g (51 mmole) of diethanolamine and 0.41 g (10.2 mmole or 0.2 mole equivalent) of sodium hydroxide. The reaction mixture was then refluxed at 110 °C for 24 hours. The compound obtained from the prior steps was evaporated under vacuum and crystallized in 200 mL of mixed organic solvents of methanol and ethyl acetate in a ratio of 1 : 1. The obtained solid product was separated and dried under vacuum before analyzed using proton-nuclear magnetic resonance spectroscopy. Dihydroxyethyl aspartate yield was 20 %.

Example 7

5 g (51 mmole) of maleic anhydride was dissolved in 10 mL of water. Then, 4.08 g (102 mmole) of sodium hydroxide was prepared in 5 mL of water. Prepared sodium hydroxide solution was dropped into prepared maleic anhydride solution at a rate of 1 mL/min. This exothermic reaction increased the reaction temperature to 80 °C rapidly. After finishing adding base solution, the temperature reaction decreased to 30 °C within 15 minutes, then stirred the reaction mixture at 30 °C for at least 1 hour, following by adding 5.36 g (51 mmole) of diethanolamine and 0.61 g (15.4 mmole or 0.3 mole equivalent) of sodium hydroxide. The reaction mixture was then refluxed at 1 10 °C for 5 hours. The compound obtained from the prior steps was evaporated under vacuum and crystallized in 200 mL of mixed organic solvents of methanol and ethyl acetate in a ratio of 1 : 1. The obtained solid product was separated and dried under vacuum before analyzed using proton-nuclear magnetic resonance spectroscopy. Dihydroxyethyl aspartate was not found.

Example 8

5 g (51 mmole) of maleic anhydride was dissolved in 10 mL of water. Then, 4.08 g (102 mmole) of sodium hydroxide was prepared in 5 mL of water. Prepared sodium hydroxide solution was dropped into prepared maleic anhydride solution at a rate of 1 mL/min. This exothermic reaction increased the reaction temperature to 80 °C rapidly. After finishing adding base solution, the temperature reaction decreased to 30 °C within 15 minutes, then stirred the reaction mixture at 30 °C for at least 1 hour, following by adding 5.36 g (51 mmole) of diethanolamine and 0.61 g (15.4 mmole or 0.3 mole equivalent) of sodium hydroxide. The reaction mixture was then refluxed at 110 °C for 15 hours. The compound obtained from the prior steps was evaporated under vacuum and crystallized in 200 mL of mixed organic solvents of methanol and ethyl acetate in a ratio of 1 : 1. The obtained solid product was separated and dried under vacuum before analyzed using proton-nuclear magnetic resonance spectroscopy. Dihydroxyethyl aspartate yield was 83 %.

Example 9

5 g (51 mmole) of maleic anhydride was dissolved in 10 mL of water. Then, 4.08 g (102 mmole) of sodium hydroxide was prepared in 5 mL of water. Prepared sodium hydroxide solution was dropped into prepared maleic anhydride solution at a rate of 1 mL/min. This exothermic reaction increased the reaction temperature to 80 °C rapidly. After finishing adding base solution, the temperature reaction decreased to 30 °C within 15 minutes, then stirred the reaction mixture at 30 °C for at least 1 hour, following by adding 5.36 g (51 mmole) of diethanolamine and 1.02 g (25.5 mmole or 0.5 mole equivalent) of sodium hydroxide. The reaction mixture was then refluxed at 1 10 °C for 15 hours. The compound obtained from the prior steps was evaporated under vacuum and crystallized in 200 mL of mixed organic solvents of methanol and ethyl acetate in a ratio of 1 :1. The obtained solid product was separated and dried under vacuum before analyzed using proton-nuclear magnetic resonance spectroscopy. Dihydroxyethyl aspartate yield was 70 %.

Example 10

5 g (51 mmole) of maleic anhydride was dissolved in 10 mL of water. Then, 4.08 g (102 mmole) of sodium hydroxide was prepared in 5 mL of water. Prepared sodium hydroxide solution was dropped into prepared maleic anhydride solution at a rate of 1 mL/min. This exothermic reaction increased the reaction temperature to 80 °C rapidly. After finishing adding base solution, the temperature reaction decreased to 30 °C within 15 minutes, then stirred the reaction mixture at 30 °C for at least 1 hour, following by adding 5.36 g (51 mmole) of diethanolamine and 0.61 g (15.4 mmole or 0.3 mole equivalent) of sodium hydroxide. The reaction mixture was then refluxed at 120 °C for 15 hours. The compound obtained from the prior step was evaporated under vacuum and crystallized in 200 mL of mixed organic solvents of methanol and ethyl acetate in a ratio of 1 : 1. The obtained solid product was separated and dried under vacuum before analyzed using proton-nuclear magnetic resonance spectroscopy. Dihydroxyethyl aspartate yield was 79 %.

Example 11

5 g (51 mmole) of maleic anhydride was dissolved in 10 mL of water. Then, 4.08 g (102 mmole) of sodium hydroxide was prepared in 5 mL water. Prepared sodium hydroxide solution was dropped into prepared maleic anhydride solution at a rate of 1 mL/min. This exothermic reaction increased the reaction temperature to 80 °C rapidly. After finishing adding base solution, the temperature reaction decreased to 30 °C within 15 minutes, then stirred the reaction mixture at 30 °C for at least 1 hour, following by adding 5.36 g (51 mmole) of diethanolamine and 1.63 g (40.8 mmole or 0.8 mole equivalent) of sodium hydroxide. The reaction mixture was then refluxed at 120 °C for 24 hours. The compound obtained from the prior step was evaporated under vacuum and crystallized in 200 mL of mixed organic solvents of methanol and ethyl acetate in a ratio of 1 : 1. The obtained solid product was separated and dried under vacuum before analyzed using pro ton- nuclear magnetic resonance spectroscopy. Dihydroxyethyl aspartate yield was 43 %.

Example 12

10 g (86 mmole) of fumaric anhydride was dissolved in 20 mL of water. Then, 6.89 g (172 mmole) of sodium hydroxide was prepared in 10 mL of water. Prepared sodium hydroxide solution was dropped into prepared fumaric anhydride solution at rate of 1 rnL/min. This exothermic reaction increased the reaction temperature to 80 °C rapidly. After finishing adding base solution, the temperature reaction decreased to 30 °C within 15 minutes, then stirred the reaction mixture at 30 °C for at least 1 hour, following by adding 9.06 g (86 mmole) of diethanolamine and 1.03 g (25.8 mmole or 0.3 mole equivalent) of sodium hydroxide. The reaction mixture was then refluxed at 1 10 °C for 24 hours. The compound obtained from the prior steps was evaporated under vacuum and crystallized in 200 mL of mixed organic solvents of methanol and ethyl acetate in a ratio of 1 :1. The obtained solid product was separated and dried under vacuum before analyzed using proton-nuclear magnetic resonance spectroscopy. Dihydroxyethyl aspartate yield was 17 %.

Example 13

10 g (86 mmole) of fumaric anhydride was dissolved in 20 mL of water. Then, 6.89 g (172 mmole) of sodium hydroxide was prepared in 10 mL of water. Prepared sodium hydroxide solution was dropped into prepared fumaric anhydride solution at a rate of 1 rriL/min. This exothermic reaction increased the reaction temperature to 80 °C rapidly. After finishing adding base solution, the temperature reaction decreased to 30 °C within 15 minutes, then stirred the reaction mixture at 30 °C for at least 1 hour, following by adding 9.06 g (86 mmole) of diethanolamine and 2.75 g (86.8 mmole or 0.8 mole equivalent) of sodium hydroxide. The reaction mixture was then refluxed at 110 °C for 24 hours. The compound obtained from the prior steps was evaporated under vacuum. Then, crystallized in 200 mL of mixed organic solvents of methanol and ethyl acetate in a ratio of 1 :1. The obtained solid product was separated and dried under vacuum before analyzed using proton-nuclear magnetic resonance spectroscopy. Dihydroxyethyl aspartate yield was 49 %.

BEST MODE OF THE INVENTION

Best mode of the invention is as disclosed in the detailed description.

Claims

1. A method for preparing diethanolamine derivatives having the structure (I):

wherein

κοο₂

— CH^

Ri represents structure (II) ^c°^2>< (II);

R₂ represents hydrogen or structure (II);

X represents hydrogen, alkali or alkaline earth metal; by reacting diethanolamine with maleic anhydride,butenedioic acid or butenedioic acid salts in the presence of alkali or alkaline earth metal hydroxide.

2. The method for preparing diethanolamine derivatives according to claim 1, wherein alkali metal hydroxide is sodium hydroxide.

3. The method for preparing diethanolamine derivatives according to claim 1 or 2, wherein alkali metal hydroxide is used in an amount of 0.2 to 0.8 mole equivalent.

4. The method for preparing diethanolamine derivatives according to any one of claims 1 to 3, wherein alkali metal hydroxide is used in an amount of 0.3 to 0.5 mole equivalent.

5. The method for preparing diethanolamine derivatives according to claim 1, wherein temperature of said method is in a range of 80 to 120 °C.

6. The method for preparing diethanolamine derivatives according to claim 5, wherein temperature of said method is in the range of 1 10 to 120 °C.

7. A diethanolamine derivative prepared from any one of claims 1 to 6 having structure (III):

wherein X represents hydrogen, alkali or alkaline earth metal.

8. The diethanolamine derivative according to claim 7, wherein the diethanolamine derivative is dihydroxyethyl aspartate.