WO2016072941A1 - Dérivés de diéthanolamine et leur procédé de préparation - Google Patents

Dérivés de diéthanolamine et leur procédé de préparation Download PDF

Info

Publication number
WO2016072941A1
WO2016072941A1 PCT/TH2015/000076 TH2015000076W WO2016072941A1 WO 2016072941 A1 WO2016072941 A1 WO 2016072941A1 TH 2015000076 W TH2015000076 W TH 2015000076W WO 2016072941 A1 WO2016072941 A1 WO 2016072941A1
Authority
WO
WIPO (PCT)
Prior art keywords
diethanolamine
mmole
sodium hydroxide
alkali
reaction
Prior art date
Application number
PCT/TH2015/000076
Other languages
English (en)
Inventor
Papapida PORNSURIYASAK
Anupat POTISATITYUENYONG
Original Assignee
Ptt Global Chemical Public Company Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from TH1401006633A external-priority patent/TH160564A/th
Application filed by Ptt Global Chemical Public Company Limited filed Critical Ptt Global Chemical Public Company Limited
Publication of WO2016072941A1 publication Critical patent/WO2016072941A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/04—Formation of amino groups in compounds containing carboxyl groups
    • C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/24—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having more than one carboxyl group bound to the carbon skeleton, e.g. aspartic acid

Definitions

  • the present invention relates to a chemical field of diethanolamine derivatives and a method for preparing said diethanolamine derivatives.
  • 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.
  • EDTA ethylenediaminetetraacetic acid
  • NTA nitrilotriacetic acid
  • degradable chelating agents produced in industrial scales are methylglycinediacetic acid (MGDA), glutamic acid ⁇ , ⁇ -diacetic acid (GLDA), iminodisuccinic acid (IDS), and dihydroxyethylglycine (DHEG).
  • 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.
  • 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.
  • this method needs a separation step of catalysts which makes the method more complicated.
  • 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.
  • This invention relates to a method for preparing diethanolamine derivatives having the structure (I):
  • Ri represents structure (II) C ° 2X (II);
  • R 2 represents hydrogen or structure (II);
  • X represents hydrogen, alkali or alkaline earth metal
  • Figure 1 shows a proton-nuclear magnetic resonance spectrum of dihydroxyethyl aspartate measured at 400 MHz by dissolving dihydroxyethyl aspartate in deuterium oxide (D 2 0), 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, 4 ⁇ , N-CH 2 x2), 3.52-3.86 (m, 7 ⁇ , 0-CH 2 x2, N-CH, N-CH-CH 2 ) ppm.
  • 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.
  • 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.
  • the present invention relates to a method for preparing diethanolamine derivatives having the structure (I):
  • Ri represents structure (II) C ° 2X (II);
  • R 2 represents hydrogen or structure (II);
  • X represents hydrogen, alkali or alkaline earth metal
  • the diethanolamine derivative has structure (III):
  • X represents hydrogen, alkali or alkaline earth metal.
  • the diethanolamine derivative is dihydroxyethyl aspartate.
  • the method for preparing diethanolamine derivative, which is dihydroxyethyl aspartate may be shown as the following.
  • butenedioic acid or butenedioic acid salts are bonded to nitrogen position of diethanolamine.
  • 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.
  • alkali or alkaline earth metal hydroxide is sodium hydroxide.
  • 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.
  • 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.
  • pH may be adjusted to be lower than 7 by adding organic acid.
  • 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 %.
  • 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 %.
  • 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.
  • 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 %.
  • 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 %.
  • 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 %.
  • 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 %.
  • 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 %.
  • the reaction mixture was then refluxed at 110 °C for 24 hours.
  • the compound obtained from the prior steps was evaporated under vacuum.
  • the obtained solid product was separated and dried under vacuum before analyzed using proton-nuclear magnetic resonance spectroscopy. Dihydroxyethyl aspartate yield was 49 %.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention concerne un procédé de préparation de dérivés de diéthanolamine répondant à la structure (I) : Formule (I) ; dans laquelle Formule (II) ; R1 représente une structure (II) R2 représente un atome d'hydrogène ou une structure (II) ; X représente un atome d'hydrogène, un métal alcalin ou alcalino-terreux ; par réaction de la diéthanolamine avec l'anhydride maléique, l'acide butènedioïque ou des sels d'acide butènedioïque en présence d'un hydroxyde de métal alcalin ou alcalino-terreux.
PCT/TH2015/000076 2014-11-05 2015-11-05 Dérivés de diéthanolamine et leur procédé de préparation WO2016072941A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TH1401006633A TH160564A (th) 2014-11-05 สารอนุพันธ์ของไดเอทาโนลามีน (Diethanolamine derivative) และกระบวนการเตรียมสารอนุพันธ์ดังกล่าว
TH1401006633 2014-11-05

Publications (1)

Publication Number Publication Date
WO2016072941A1 true WO2016072941A1 (fr) 2016-05-12

Family

ID=55221481

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/TH2015/000076 WO2016072941A1 (fr) 2014-11-05 2015-11-05 Dérivés de diéthanolamine et leur procédé de préparation

Country Status (1)

Country Link
WO (1) WO2016072941A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018226169A3 (fr) * 2017-06-05 2019-05-02 Ptt Global Chemical Public Company Limited Agent chélatant à base de dérivé de diéthanolamine biodégradable et son procédé de préparation

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0591934A1 (fr) * 1992-10-05 1994-04-13 Fuji Photo Film Co., Ltd. Composition et méthode de traitement photographique
JPH08208569A (ja) 1995-02-03 1996-08-13 Nippon Shokubai Co Ltd 洗剤組成物
EP1086944A2 (fr) * 1999-09-03 2001-03-28 Nippon Shokubai Co., Ltd. Composition de dérivés d'amino-acide et procédé pour la préparation d'un dérivé d'amino-acide
US6590120B1 (en) 1998-03-09 2003-07-08 Kemira Chemicals Oy Methods for the preparation of an N-bis-[2-(1,2-dicarboxy-ethoxy)-ethyl]amine derivative and products of the methods and their uses

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0591934A1 (fr) * 1992-10-05 1994-04-13 Fuji Photo Film Co., Ltd. Composition et méthode de traitement photographique
JPH08208569A (ja) 1995-02-03 1996-08-13 Nippon Shokubai Co Ltd 洗剤組成物
US6590120B1 (en) 1998-03-09 2003-07-08 Kemira Chemicals Oy Methods for the preparation of an N-bis-[2-(1,2-dicarboxy-ethoxy)-ethyl]amine derivative and products of the methods and their uses
EP1086944A2 (fr) * 1999-09-03 2001-03-28 Nippon Shokubai Co., Ltd. Composition de dérivés d'amino-acide et procédé pour la préparation d'un dérivé d'amino-acide
US6504054B1 (en) 1999-09-03 2003-01-07 Nippon Shokubai Co., Ltd. Amino acid derivative and producing method thereof
EP1086944B1 (fr) 1999-09-03 2005-05-25 Nippon Shokubai Co., Ltd. Composition de dérivés d'amino-acide et procédé pour la préparation d'un dérivé d'amino-acide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PROBLEMY KHIMII KOMPLEKSONOV, 1985, pages 108 - 115

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018226169A3 (fr) * 2017-06-05 2019-05-02 Ptt Global Chemical Public Company Limited Agent chélatant à base de dérivé de diéthanolamine biodégradable et son procédé de préparation

Similar Documents

Publication Publication Date Title
EP3196196B1 (fr) Procédé de préparation de calcobutrol
CN101445477A (zh) N-取代的马来酰亚胺类的制备方法
WO2016072941A1 (fr) Dérivés de diéthanolamine et leur procédé de préparation
WO2018226169A2 (fr) Agent chélatant à base de dérivé de diéthanolamine biodégradable et son procédé de préparation
CN107743480B (zh) 制备酚乙二胺二乙酸化合物的方法
WO2019049824A1 (fr) Dérivé de l-carnosine protégé, l-carnosine et procédé de production d'un complexe l-carnosine-zinc cristallin
US11225456B2 (en) Process for the preparation of a mixture of chelating agents, mixture of chelating agents and methods of using them
JPH09194448A (ja) 二分子のアミノ酸の連結によるジアミン型ポリアミノ酸の製造方法およびそれらを含む生分解性キレート剤
TW201544525A (zh) 含聚烷氧基醇之（甲基）丙烯酸酯之製備
EP3645506B1 (fr) Procédé de préparation d'un mélange d'agents chélatants, mélange d'agents chélatants et procédés d'utilisation de ceux-ci
US10494329B2 (en) Method for synthesizing tetraalkylnitriloacetic acid diacetamide compound
CN102933542B (zh) 环状碳二亚胺化合物的中间体的制造方法
JPH1059910A (ja) アミノジカルボン酸−ｎ，ｎ−二酢酸塩類の製造法
KR102425274B1 (ko) 5-(c1~c4 알킬) 테트라졸의 합성방법
US920306A (en) Strontium salt of dibrom-behenic acid.
CN109928888A (zh) 一种西格列汀中间体的制备方法
JP4759809B2 (ja) ジアルキルエチレンジアミンジマロン酸類、その製造法及びその用途
JP5248132B2 (ja) カリックスアレン誘導体の製造方法
KR20200009001A (ko) 디아미노벤젠 화합물의 제조 방법
JPS59225147A (ja) Ｏ−置換−ヒドロキシルアミンを製造する方法
JP4024350B2 (ja) アリルアミン誘導体およびその製造方法
CN114195646A (zh) 一种1-氯-4-(6-硝基环己-3-烯基)-苯的制备方法
CN107556256A (zh) 5‑(c1~c4烷基)四唑的合成方法
JPH09157244A (ja) Ｎ，ｎ−ビス（ヒドロキシアルキル）スルファミン酸 金属塩の製造法
JPH02288850A (ja) Ｎ，ｎ―ジ置換アニリン類の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15828399

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15828399

Country of ref document: EP

Kind code of ref document: A1