WO2001034560A2 - Verfahren zur herstellung von iminodicarbonsäuren - Google Patents
Verfahren zur herstellung von iminodicarbonsäuren Download PDFInfo
- Publication number
- WO2001034560A2 WO2001034560A2 PCT/EP2000/011092 EP0011092W WO0134560A2 WO 2001034560 A2 WO2001034560 A2 WO 2001034560A2 EP 0011092 W EP0011092 W EP 0011092W WO 0134560 A2 WO0134560 A2 WO 0134560A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carried out
- mol
- acid
- salt
- amidocarbonylation
- Prior art date
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
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IL14949700A IL149497A0 (en) | 1999-11-11 | 2000-11-09 | Method for producing iminodicarboxylic acids |
AU18562/01A AU1856201A (en) | 1999-11-11 | 2000-11-09 | Method for producing iminodicarboxylic acids |
EP00981245A EP1228036A2 (de) | 1999-11-11 | 2000-11-09 | Verfahren zur herstellung von iminodicarbonsäuren |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19954194A DE19954194A1 (de) | 1999-11-11 | 1999-11-11 | Verfahren zur Herstellung von Iminodicarbonsäuren und deren Verwendung |
DE19954194.9 | 1999-11-11 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2001034560A2 true WO2001034560A2 (de) | 2001-05-17 |
WO2001034560A3 WO2001034560A3 (de) | 2001-12-13 |
Family
ID=7928639
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2000/011092 WO2001034560A2 (de) | 1999-11-11 | 2000-11-09 | Verfahren zur herstellung von iminodicarbonsäuren |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP1228036A2 (de) |
CN (1) | CN1390195A (de) |
AU (1) | AU1856201A (de) |
DE (1) | DE19954194A1 (de) |
IL (1) | IL149497A0 (de) |
WO (1) | WO2001034560A2 (de) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998004518A1 (de) * | 1996-07-25 | 1998-02-05 | Aventis Research & Technologies Gmbh & Co Kg | Verfahren zur katalytischen herstellung von n-acylglycinderivaten |
WO1998035930A1 (en) * | 1997-02-13 | 1998-08-20 | Monsanto Company | Method of preparing amino carboxylic acids |
-
1999
- 1999-11-11 DE DE19954194A patent/DE19954194A1/de not_active Withdrawn
-
2000
- 2000-11-09 AU AU18562/01A patent/AU1856201A/en not_active Abandoned
- 2000-11-09 WO PCT/EP2000/011092 patent/WO2001034560A2/de not_active Application Discontinuation
- 2000-11-09 IL IL14949700A patent/IL149497A0/xx unknown
- 2000-11-09 CN CN00815518.6A patent/CN1390195A/zh active Pending
- 2000-11-09 EP EP00981245A patent/EP1228036A2/de not_active Withdrawn
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998004518A1 (de) * | 1996-07-25 | 1998-02-05 | Aventis Research & Technologies Gmbh & Co Kg | Verfahren zur katalytischen herstellung von n-acylglycinderivaten |
WO1998035930A1 (en) * | 1997-02-13 | 1998-08-20 | Monsanto Company | Method of preparing amino carboxylic acids |
Also Published As
Publication number | Publication date |
---|---|
IL149497A0 (en) | 2002-11-10 |
CN1390195A (zh) | 2003-01-08 |
DE19954194A1 (de) | 2001-05-17 |
EP1228036A2 (de) | 2002-08-07 |
WO2001034560A3 (de) | 2001-12-13 |
AU1856201A (en) | 2001-06-06 |
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