EP2819991A1 - Procédé de synthèse d'esters/éthers entre des dérivés d'acides gras et des acides hydroxycarboxyliques - Google Patents

Procédé de synthèse d'esters/éthers entre des dérivés d'acides gras et des acides hydroxycarboxyliques

Info

Publication number
EP2819991A1
EP2819991A1 EP13708762.3A EP13708762A EP2819991A1 EP 2819991 A1 EP2819991 A1 EP 2819991A1 EP 13708762 A EP13708762 A EP 13708762A EP 2819991 A1 EP2819991 A1 EP 2819991A1
Authority
EP
European Patent Office
Prior art keywords
acid
fatty acid
reaction
emo
acid derivatives
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP13708762.3A
Other languages
German (de)
English (en)
Inventor
Hans-Josef Altenbach
Bernd Jakob
Hans-Willi Kling
Kartsen LANGE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bergische Universitaet Wuppertal
Original Assignee
Bergische Universitaet Wuppertal
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
Application filed by Bergische Universitaet Wuppertal filed Critical Bergische Universitaet Wuppertal
Publication of EP2819991A1 publication Critical patent/EP2819991A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
    • C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
    • C08G59/186—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents with acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
    • C09F7/00—Chemical modification of drying oils
    • C09F7/10—Chemical modification of drying oils by re-esterification
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom

Definitions

  • the present invention relates to the synthesis of fatty acid derivatives, in particular of fatty acid derivatives, from the reaction of epoxidized fatty acid derivatives with
  • Hydroxypolycarboxylic arise. Such compounds are of industrial interest because they may i.a. when
  • Emulsifiers or surfactants, lubricant additives, complexing agents or polymeric materials are used.
  • the advantages are the good compatibility (non-toxic, non-irritating to the skin), the biological degradation work and their production starting from
  • Fatty acid derivatives with hydroxypolycarboxylic acids proposed, containing the step a) reaction of epoxidized fatty acid derivatives with hydroxypolycarboxylic acids in the presence of boric acid and / or at least one boronic acid
  • Compounds can be produced in high yields.
  • fatty acid derivatives obtainable from the reaction of epoxidized fatty acid derivatives with hydroxypolycarboxylic acids are provided.
  • epoxidized fatty acid derivatives are understood in particular to mean the following compounds or mixtures thereof: a) epoxidized fatty acids, for example of oleic acid, ricinoleic acid, erucic acid, linoleic acid, linolenic acid, preferably oleic acid
  • epoxidized fatty acid esters for example of oleic acid, ricinoleic acid, erucic acid, linoleic acid, linolenic acid as their alkyl esters, e.g. Methyl ester, ethyl ester
  • epoxidized triglycerides for example of soybean oil, rapeseed oil, sunflower oil, olive oil, castor oil,
  • alkyl glycidyl ether preferred alkyl chain length C8-C24
  • hydroxypolycarboxylic acids are meant compounds having at least two
  • Compounds are: malic acid, tartaric acid, citric acid, mucic acid, glucaric acid.
  • boric acid in the sense of the invention means any boron compound which reacts under the particular reaction conditions at least partially to form boric acid or the boron-hydroxycarboxylic acid complex described above
  • Preferred boronic acids are (due to their increased stability) arylboronic acids or
  • Heteroarylboronic It has been found that especially nitro, methoxy and fluorine-substituted (also trifluoromethyl-substituted) phenylboronic acids are particularly effective, so these are particularly preferred. Particularly preferred are 3- Nitrophenylboronic acid, 4-methoxyphenylboronic acid, 4-trifluoromethyl-phenylboronic acid, and 3-trifluoromethyl-phenylboronic acid and 3-thiophenylboronic acid and mixtures of these acids. Of course, the boronic acid may also be suitable, analogous to boric acid
  • boronic acid in the sense of the invention means any boron compound which under the particular reaction conditions at least partially reacts to form a boronic acid.
  • the reaction can of course also be carried out with a mixture of boric acid and
  • the boric acid and / or the boronic acid in step a) in a molar fraction of> 0.5 to ⁇ 60%, preferably> 1% to ⁇ 40%, more preferably> 2 to ⁇ 20%, based on the hydroxypolycarboxylic acid used.
  • This procedure has proven itself in practice, since such a speedy implementation takes place.
  • step a) takes place in the presence of an aprotic solvent, preferably selected from the group consisting of ethyl acetate, tetrahydrofuran, diethyl ether, methyl tert-butyl ether, 1,4-dioxane, N, N-dimethylformamide, dimethyl sulfoxide, 1,2-dichloroethane, acetone, ⁇ , ⁇ -dimethylacetamide, dimethoxyethane, more preferably t-butanol, chlorobenzene, toluene, hexane, o-dichlorobenzene, more preferably THF, acetone and 1,4-dioxane or mixtures thereof.
  • an aprotic solvent preferably selected from the group consisting of ethyl acetate, tetrahydrofuran, diethyl ether, methyl tert-butyl ether, 1,4-dioxane,
  • the recovery of the reaction product can be carried out in various ways and also depends on its physical properties such as melting point or solubility.
  • EMO electronic grade
  • citric acid memory
  • boric acid boric acid
  • 20 ml of EtOAc were added, then 2 ⁇ with 20 ml of 1 N HCl, and 1 ⁇ with 20 ml of sat. Shaken out NaCl, the organic phase dried over Na 2 S0 4 and concentrated in vacuo (rotary evaporator). Obtained were 0.7 g of a colorless oil.
  • EMO electronic grade
  • a solution of 781 mg of citric acid and 15 mg of boric acid in 3 ml of dioxane was slowly added dropwise.
  • the solution was stirred at RT for 24 h (starting material EMO no longer detectable in the TLC).
  • 20 ml of EtOAc were added, then in each case 2x with 20 ml of 1 N HCl and 1 x with 20 ml of sat. Shaken out NaCl. It was dried over Na 2 S0 4 and concentrated on a rotary evaporator. 0.95g was obtained as a colorless oil.
  • the proton signals of the citric acid are 3.05-2.78 ppm, as a result of which an average of 0.5 citric acid molecules were incorporated per molecule.
  • Example 5 Reaction of EMO with citric acid in THF 2.3 g of EMO (technical grade) were placed in a 25 ml round bottomed flask and cooled to 0 ° C. A solution of 2.9 g of citric acid and 45 mg of boric acid in 9 ml of THF was slowly added dropwise under argon. The solution was stirred at RT for 24 h. Then the reaction mixture 50 ml EtOAc was added and 2x with 50 ml of IN HCl and lx with 50 ml sat. Shaken out NaCl. After drying over MgSO 4 , filtering and concentrating on the rotary evaporator, 3.74 g of a colorless, highly viscous oil were obtained.
  • Example 7 Reaction of EMO with malic acid in dioxane 781 mg of EMO (technical grade) were initially charged in a 25 ml round bottom flask and cooled to 0 ° C. A solution of 671 mg of malic acid and 15 mg of boric acid in 3 ml of dioxane was slowly added dropwise under argon. It was stirred for 24 h at RT (starting material EMO no longer detectable in the DC). 20 ml of EtOAc were added and 2x with 20 ml of IN HCl and 1 x with 20 ml ges. Shaken out NaCl. It was dried over NaS0 4 and concentrated in vacuo on a rotary evaporator. Yield: 0.76 of a colorless oil.
  • the proton signals of the citric acid are at 3.04-2.82 ppm, as a result of which 2.5 citric acid molecules per molecule were incorporated on average.
  • Example 13 Reaction of ESO with malic acid 0.9 g of malic acid and 2.5 mg of boric acid were dissolved in 3.5 ml of THF and slowly added with 0.7 g of Edenol T40. The reaction mixture was stirred for 24 h at room temperature (starting material ESO no longer detectable in the TLC). 20 ml of EtOAc were added and in each case 2x with 20 ml of 1N HCl, and 1 ⁇ with 20 ml of sat. Shaken out NaCl solution. It was then dried over MgS0 4 , filtered and the solvent removed on a rotary evaporator. There were obtained 0.97 g as a colorless oil.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de synthèse ciblée pour la liaison de dérivés d'acides gras époxydés à des acides hydroxypolycarboxyliques en présence d'acide borique ou d'acides boroniques.
EP13708762.3A 2012-03-01 2013-02-28 Procédé de synthèse d'esters/éthers entre des dérivés d'acides gras et des acides hydroxycarboxyliques Withdrawn EP2819991A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201210101736 DE102012101736A1 (de) 2012-03-01 2012-03-01 Verfahren zur Synthese von Estern/Ethern zwischen Fettsäurederivaten und Hydroxycarbonsäuren
PCT/EP2013/054100 WO2013127960A1 (fr) 2012-03-01 2013-02-28 Procédé de synthèse d'esters/éthers entre des dérivés d'acides gras et des acides hydroxycarboxyliques

Publications (1)

Publication Number Publication Date
EP2819991A1 true EP2819991A1 (fr) 2015-01-07

Family

ID=47845981

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13708762.3A Withdrawn EP2819991A1 (fr) 2012-03-01 2013-02-28 Procédé de synthèse d'esters/éthers entre des dérivés d'acides gras et des acides hydroxycarboxyliques

Country Status (3)

Country Link
EP (1) EP2819991A1 (fr)
DE (1) DE102012101736A1 (fr)
WO (1) WO2013127960A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019158411A1 (fr) 2018-02-14 2019-08-22 Basf Se Utilisation de 1,2-alcanediols comme améliorants de mousse pour des tensioactifs à base d'esters d'acide citrique comprenant des alcools éthoxylés
WO2019158409A1 (fr) 2018-02-14 2019-08-22 Basf Se Procédé de production de condensats tensioactifs d'acide citrique et produits obtenus par ce procédé
CN110642719A (zh) * 2019-10-12 2020-01-03 江南大学 一种苹果酸基环保增塑剂的制备方法及其应用

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE517875A (fr) * 1952-02-25
US3180749A (en) * 1961-11-06 1965-04-27 Swift & Co Water soluble polymers of epoxidized fats
DE1961861B2 (de) * 1969-12-10 1973-03-15 Dynamit Nobel Ag, 5210 Troisdorf Verfahren zur gewinnung von hellen, farbstabilen fettsaeuren
DE2926635A1 (de) * 1979-07-02 1981-01-15 Henkel Kgaa Verfahren zur reinigung von fettsaeure- oder fettsaeureestergemischen
DE19526501A1 (de) * 1995-07-20 1997-01-23 Basf Ag Hydroxymischether durch Ringöffnung von Epoxiden ungesättigter Fettsäureester mit Polyglykolethern und ihre Verwendung als biologisch abbaubarer Entschäumer
DE10333336A1 (de) * 2003-07-23 2005-02-17 Dracowo Forschungs- Und Entwicklungs Gmbh In situ Beschichtungsmassen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2013127960A1 *

Also Published As

Publication number Publication date
DE102012101736A1 (de) 2013-09-05
WO2013127960A1 (fr) 2013-09-06

Similar Documents

Publication Publication Date Title
EP2759529B1 (fr) Procédé de préparation de 1-palmitoyl-3-acétylglycérol et procédé de préparation de 1-palmitoyl-2-linoléoyl-3-acétylglycérol l'utilisant
DE3527241A1 (de) Verfahren zur herstellung von 3-substituierten derivaten von 1-amino-2-hydroxy-propan
JP2016504404A (ja) ピリピロペン化合物の製造方法
EP2819991A1 (fr) Procédé de synthèse d'esters/éthers entre des dérivés d'acides gras et des acides hydroxycarboxyliques
DE102011054602A1 (de) Verfahren zur Synthese von Citronensäureestern
DE2727805A1 (de) Verfahren zur herstellung von oxynormorphon
CN110551133A (zh) 叔丁基-5-(羟甲基)-7-氧杂-2-氮杂螺[3.5]壬烷-2-甲酸基酯的制法
CN113461643A (zh) 一种4-甲基苯磺酸[(3-氟氧杂环丁烷-3-基)甲基]酯的合成方法
CN108997229B (zh) 1,2,3,4-四氢喹喔啉-6-羧酸甲酯及其制备方法
CN109422654B (zh) 合成脂肪胺甲基化化合物的方法
EP3452446B1 (fr) Procédé pour la preparation des derivés de spirocyclique 1-h-pyrrolidin-2,4-dione substitués par cis-alkoxy
EP2170791B1 (fr) Procede de production de cyclopent-4-ene-1,3-diol ou de derives de cyclopent-4-ene-1,3-diol
US20170008902A1 (en) Improved glycol acylation process with water-tolerant metal triflates
EP1763497B1 (fr) Procede pour produire des alcenes par elimination d'eau a partir d'alcools au moyen d'anhydrides d'acide alkylphosphonique
KR101777633B1 (ko) 베라프로스트 제조 중간체의 제조방법
US20150299107A1 (en) Selective extraction of an omega-functionalized acid after oxidative cleavage of an unsaturated fatty acid and derivatives
KR20160141950A (ko) 1-메틸-2-(2-하이드록시에틸)피롤리딘의 상업생산이 가능한 효과적인 합성방법
KR20060044536A (ko) 글리세롤 유도체의 위치 선택적인 제조방법 및 그 중간체
DE3126014C2 (de) Verfahren zur Herstellung von Chromon
DE930565C (de) Verfahren zur Herstellung von 1-Phenyl-2-amino-1, 3-propandiolen oder von im Phenylrest substituierten 1-Phenyl-2-amino-1, 3-propandiolen
DE2059296C3 (de) Verfahren zur Herstellung von Estern der 3-Methylflavon-8-carbonsäure mit N-tert-Aminoalkoholen
UA127368C2 (uk) Спосіб одержання трициклічної сполуки і її проміжного продукту
DE19737329A1 (de) Verfahren zur Herstellung von Chlorameisensäureestern
AT390789B (de) Enantiomerenreine zwischenprodukte, deren herstellung und deren verwendung zur herstellung von enantiomerenreinem disparlure
KR20230066851A (ko) 테트라히드로퓨란-2,5-디메탄올을 사용한 테트라히드로퓨란-2,5-디에스터의 제조 및 분리 정제 방법

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20140806

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20161207

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20170419