EP1228036A2 - Procede de production d'acides iminodicarboxyliques - Google Patents

Procede de production d'acides iminodicarboxyliques

Info

Publication number
EP1228036A2
EP1228036A2 EP00981245A EP00981245A EP1228036A2 EP 1228036 A2 EP1228036 A2 EP 1228036A2 EP 00981245 A EP00981245 A EP 00981245A EP 00981245 A EP00981245 A EP 00981245A EP 1228036 A2 EP1228036 A2 EP 1228036A2
Authority
EP
European Patent Office
Prior art keywords
carried out
mol
acid
salt
amidocarbonylation
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Withdrawn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
EP00981245A
Other languages
German (de)
English (en)
Inventor
Harald GRÖGER
Benedikt Hammer
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.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
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 Degussa GmbH filed Critical Degussa GmbH
Publication of EP1228036A2 publication Critical patent/EP1228036A2/fr
Withdrawn legal-status Critical Current

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
    • C07C227/12—Formation of amino and carboxyl groups

Definitions

  • the present invention relates to a process for the preparation of iminodicarboxylic acids
  • Amino and iminodicarboxylic acids like the corresponding monocarboxylic acids, are generally to be classified as important starting compounds for pharmaceuticals, agrochemical compounds and pesticides
  • N-phosphonomethyl-glycm is based in particular on immodiacetic acid (IDA), which can in the meantime be converted into the desired product via numerous described synthetic routes. Among other things, it can be reacted with formaldehyde and phosphorous acid or phosphorus chloride to form N-phosphonomethyliminodiacetic acid and sodium chloride. the substituted immodiacetic acid obtained in this way is then oxidatively split, for example in the presence of a carbon-containing catalyst, to give the corresponding acid form of N-phosphonomethylglycine
  • IDA immodiacetic acid
  • Immodiacetic acid therefore plays a central role in a wide variety of synthetic routes to glyphosate
  • IDA iminodiacetonitrile
  • sodium hydroxide solution sodium salt of immodiacetic acid (Na DA) followed by ⁇ mer neutralization with a strong mineral acid, for example hydrochloric acid or sulfuric acid.
  • a strong mineral acid for example hydrochloric acid or sulfuric acid.
  • hydrochloric acid at least two equivalent sodium chlorides are also obtained as waste in addition to the desired immodic acid
  • N-protected Immodiacetic Acid N-Acyl-IDA
  • WO 98/35 930 describes the reaction of a carbamoyl compound with the precursor of a carboxymethylation catalyst.
  • Amides are typical carbamoyl compounds.
  • Urea and carbamates mentioned All compounds should be used as catalyst precursors can, which contain a metal from group VIII of the Periodic Table of the Elements and which are suitable for carboxymethylation reactions, with cobalt-containing catalysts in particular being a prerequisite for the reaction.
  • the use of a gas mixture consisting of carbon monoxide and hydrogen is a prerequisite 98/35 930 in principle also with the Pd catalyst systems known hitherto from amidomonocarbonylation.
  • Heterogeneous Pd catalysts have never been used for an amidodicarboxylation reaction, since heterogeneous catalysts usually run in completely different mechanistic ways.
  • a recently published work shows the suitability of heterogeneous Pd / C- Catalysts for amidomonocarbon changes (Beller et al Tetrahedron Letters, 1999, 40, S 4523-4526)
  • the object of the present invention was therefore to develop a process for the preparation of iminodicarboxylic acids, which is usually carried out by amidocarbonylation of compounds of the formula
  • R H, NH 2 , 28 alkyl, C 6 12 aryl with carbon monoxide in an acidic medium in the presence of a catalytic
  • Palladium complex and an aldehyde and the final hydrolytic cleavage of the N-acyl group is carried out, but which is independent of the strict reaction conditions such as an absolute absence of water and / or high pressures of at least 100 bar and / or the specification of selected organic solvents
  • the reaction according to the invention succeeds particularly efficiently when the molar proportion of water contained in the reaction medium is between 0.001 aquiv and 10 aquiv, based on the molar amount of aldehyde used and preferably 0.01 aquiv and 4 aquiv
  • Formamide, acetamide or urea have proven to be particularly suitable as a starting material from the range of all possible compounds according to claim 1
  • An inorganic palladium (II) salt such as palladium bromide and chlorine, which is used in quantities of 0.01 to 0.25 mol% based on the amount of amide component used, is a preferred representative of the required catalytic palladium complex
  • heterogeneous Pd catalysts such as Pd / C have also proven to be very efficient
  • the present invention provides for the use of a mineral acid, in particular sulfuric acid, as the acid
  • Mineral acids are also used by the present invention for the catalytic system which contains a Pd compound as a further component, preferably a hydrogen halide acid such as, for example, hydrobromic acid and in particular a 48% HBr should be used
  • Formaldehyde, benzaldehyde and cyclohexane carbaldehyde and in particular a 30% form solution are provided, which is advantageous in practice has proven. to use the amide and aldehyde components in a stochiometric ratio of 2 to 2.5 1
  • the reaction according to the present invention can be increased further by carrying it out in the presence of max. 35 mol% of a halogen salt, for which bromide salts in particular seem to be suitable.
  • the halogen salts can also be an alkali halogen salt, which in particular a lithium.
  • Sodium and potassium salts can represent
  • the flow of halogen salt is particularly favorable when it is used in an amount of max. 10 mol% and in particular in proportions of 5 mol%
  • the reaction conditions are to be selected such that the amido carbonylation is preferably carried out at a carbon monoxide pressure of 20 to 80 bar and in particular at 40 to 60 bar, the preferred temperature for the carbonylation reaction should according to the invention between 30 and 120 ° C and in particular at 60 to 80 ° C.
  • composition of the carbonylation gas is completely uncritical for the success of the present process. Although it may be of advantage if the carbon monoxide used is used in a remainder of the form, gas mixtures which contain the carbon monoxide only in the required amounts are sufficient for most applications
  • amidocarbonation is carried out in a water-containing medium.
  • this does not completely rule out the absence of organic solvents, which is why the invention provides process variants for certain reaction procedures in which the production of the iminodicarboxylic acids in an organic process water-containing solvent is carried out, with acetone (ACCN) and N-methylpyrrohdon (NMP) being of particular concern

Landscapes

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

Abstract

L'invention concerne un procédé de production d'acides iminodicarboxyliques par amidocarbonylation de composés correspondants à la formule (I), où R représente H, NH2, alkyle C1-C28, aryle C6-C12, avec du monoxyde de carbone, en milieu acide, en présence d'un complexe de palladium catalytique et d'un aldéhyde, et par fission hydrolitique consécutive du groupe N-acyle. Ce procédé se caractérise par le fait que l'amidocarbonylation est réalisée dans un milieu aqueux. Comme matériau de départ conviennent particulièrement le formamide, l'acétamide ou l'urée. Des sels de Pd(II) inorganiques, tels que l'acétate de palladium ou le chlorure de palladium, ou bien des catalyseurs au Pd hétérogènes sont avant tout utilisés dans des mélanges comprenant un acide minéral et dans des proportions pouvant aller de 0,01 à 0,25 % en moles, le système catalytique devant contenir en particulier de l'acide bromique ou de l'acide muriatique. Il est également prévu que la réaction se fasse en présence d'au maximum 35 % en moles d'un sel d'halogénure.
EP00981245A 1999-11-11 2000-11-09 Procede de production d'acides iminodicarboxyliques Withdrawn EP1228036A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19954194 1999-11-11
DE19954194A DE19954194A1 (de) 1999-11-11 1999-11-11 Verfahren zur Herstellung von Iminodicarbonsäuren und deren Verwendung
PCT/EP2000/011092 WO2001034560A2 (fr) 1999-11-11 2000-11-09 Procede de production d'acides iminodicarboxyliques

Publications (1)

Publication Number Publication Date
EP1228036A2 true EP1228036A2 (fr) 2002-08-07

Family

ID=7928639

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00981245A Withdrawn EP1228036A2 (fr) 1999-11-11 2000-11-09 Procede de production d'acides iminodicarboxyliques

Country Status (6)

Country Link
EP (1) EP1228036A2 (fr)
CN (1) CN1390195A (fr)
AU (1) AU1856201A (fr)
DE (1) DE19954194A1 (fr)
IL (1) IL149497A0 (fr)
WO (1) WO2001034560A2 (fr)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19629717C1 (de) * 1996-07-25 1998-02-12 Hoechst Ag Verfahren zur katalytischen Herstellung von N-Acylglycinderivaten
JP2001511810A (ja) * 1997-02-13 2001-08-14 モンサント カンパニー アミノカルボン酸の製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0134560A3 *

Also Published As

Publication number Publication date
WO2001034560A2 (fr) 2001-05-17
AU1856201A (en) 2001-06-06
DE19954194A1 (de) 2001-05-17
WO2001034560A3 (fr) 2001-12-13
IL149497A0 (en) 2002-11-10
CN1390195A (zh) 2003-01-08

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