EP0287885B1 - Process for the preparation of serine-n,n-diacetic acid and its derivatives - Google Patents
Process for the preparation of serine-n,n-diacetic acid and its derivatives Download PDFInfo
- Publication number
- EP0287885B1 EP0287885B1 EP88105376A EP88105376A EP0287885B1 EP 0287885 B1 EP0287885 B1 EP 0287885B1 EP 88105376 A EP88105376 A EP 88105376A EP 88105376 A EP88105376 A EP 88105376A EP 0287885 B1 EP0287885 B1 EP 0287885B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- serine
- mol
- salt
- alkali metal
- 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title description 8
- 238000002360 preparation method Methods 0.000 title description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- -1 alkali metal salt Chemical class 0.000 claims description 7
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000002560 nitrile group Chemical group 0.000 claims description 3
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 239000008139 complexing agent Substances 0.000 abstract description 18
- 239000003599 detergent Substances 0.000 abstract description 11
- 239000007844 bleaching agent Substances 0.000 abstract description 7
- 239000003381 stabilizer Substances 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 229910001385 heavy metal Inorganic materials 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- 238000009472 formulation Methods 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229960001153 serine Drugs 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000004061 bleaching Methods 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000012459 cleaning agent Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229960001922 sodium perborate Drugs 0.000 description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000007059 Strecker synthesis reaction Methods 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N anhydrous trimethylamine Natural products CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- UETZVSHORCDDTH-UHFFFAOYSA-N iron(2+);hexacyanide Chemical compound [Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] UETZVSHORCDDTH-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000001863 plant nutrition Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3937—Stabilising agents
- C11D3/394—Organic compounds
Definitions
- the invention relates to a process for the preparation of serine-N, N-diacetic acid and derivatives and the intermediate product serine-N, N-diacetonitrile for the production of serine-N, N-diacetic acid and its salts.
- the object of the present invention is to provide complexing agents for alkaline earth and heavy metal ions for a wide variety of technical fields, in particular for detergents, which, in addition to good complexing properties, are ecologically harmless, contain no phosphorus if possible and are readily biodegradable.
- a technically advantageous manufacturing process is to be developed for these complexing agents.
- serine-N, N-diacetic acid in the form of the free acid or in particular the sodium, potassium, ammonium or organic amine salts are excellent complexing agents for calcium, magnesium and iron, copper, nickel and manganese ions represent, while the acid derivatives, especially amides, esters and the nitriles are preferred intermediates for the preparation of the acid and its salts.
- the invention therefore relates to a process for the preparation of compounds of the formula I.
- Y represents the radical -COOH, which is optionally in the form of an alkali metal, ammonium or substituted ammonium salt, or represents the radical -CN and X is a hydroxyl group, the carboxylic acid group thereby present optionally being in the form of an alkali metal, ammonium or substituted ammonium salt, or a radical -NR3R4, in which R3 and R4 are identical or different and represent a hydrogen atom or an alkyl radical with 1 to 4 C.
- -Atoms stand, means by 1 mol of serine (3-hydroxy-2-aminopropionic acid), optionally in the form of an alkali salt or acid amide, optionally substituted on the amide nitrogen atom by one or two alkyl radicals having 1 to 4 carbon atoms, in water, an organic solvent or their mixtures with 2.0 to 2.6 mol of formaldehyde and 2.0 to 2.3 mol of liquid hydrocyanic acid at temperatures from 0 to 45 ° C. or with 2.0 to 2.3 mol of alkali metal cyanide at temperatures from 40 to 100 ° C and, if appropriate, hydrolyze the amide and nitrile groups present in the presence of an acid or base and, if appropriate, isolate the free acid or a salt of the formula I.
- the free serine N, N-diacetic acid and the sodium, potassium and ammonium salts in particular the trisodium, tripotassium and triammonium salt, and organic triamine salts with a tertiary nitrogen atom are to be mentioned in particular.
- the bases on which the organic amine salts are based are, in particular, tertiary amines, such as trialkylamines having 1 to 4 carbon atoms in the alkyl, such as trimethyl and triethylamine, and trialkanolamines having 2 or 3 carbon atoms in the alkanol radical, preferably triethanolamine and tripropanolamine.
- tertiary amines such as trialkylamines having 1 to 4 carbon atoms in the alkyl, such as trimethyl and triethylamine, and trialkanolamines having 2 or 3 carbon atoms in the alkanol radical, preferably triethanolamine and tripropanolamine.
- the preferred starting compound is serine in the form of its racemic mixture and optionally in the form of the sodium, potassium or ammonium salt.
- Water is preferably used as the solvent, or organic solvents which are miscible with water, such as methanol, ethanol, n-propanol, isopropanol, tertiary butanol, dioxane or tetrahydrofuran. Mixtures of these organic solvents with one another or their mixtures with water can also be used. In the case of aqueous mixtures, 10 to 70% by weight of organic solvent is expediently added to the weight of the water.
- the concentration of the starting compounds in the respective solvent is advantageously 10 to 80% by weight, preferably 20 to 70% by weight.
- the sodium or potassium salt of the serine in one of the abovementioned solvents or solvent mixtures with an aqueous solution being preferred, with the formaldehyde in the form of its aqueous, about 30% by weight solution and the liquid hydrocyanic acid the preferred temperatures of 15 to 25 ° C implemented.
- reaction with akalicyanide in particular sodium or potassium cyanide, is preferably carried out at 70 to 100 ° C. instead of the liquid hydrocyanic acid.
- hydrolysis or saponification to give the carboxylic acid is carried out in a conventional manner in an aqueous reaction mixture, if appropriate after adding water in the presence of alkalis, such as sodium or potassium hydroxide, or of acid such as sulfuric or hydrochloric acid.
- This hydrolysis is expediently carried out at temperatures from 20 to 110 ° C., preferably 40 to 100 ° C., with a slight excess of base or acid, if necessary.
- the serine-N, N-diacetic acid or an alkali salt is preferably obtained. Then salts with another cation can be prepared without further notice.
- an acid derivative can also be produced in the usual way from the acid obtained.
- the compounds of formula I can be isolated in pure form without difficulty. Spray or freeze drying, crystallization or precipitation are particularly suitable for the free acid and the salts. It can be advantageous to use the resulting solution directly for technical use.
- the production process according to the invention has the advantage over known processes, in particular for the production of serine-N, N-diacetic acid and its salts, that there is practically no inorganic salt load. Due to the easy availability of the starting compounds, extremely inexpensive large-scale processes are made available.
- the serine-N, N-diacetic acid and its salts produced by the invention are outstandingly suitable for complexing alkaline earth and heavy metal ions, in particular calcium, magnesium as well as iron, copper, nickel and manganese ions. Because of this ability, they have one Variety of technical applications. Since they are biodegradable compounds, they can be used in large quantities wherever the waste water has to be clarified and phosphorus-containing compounds should also be avoided.
- the complexing agents mentioned can be used in washing and cleaning agents in order to control the content of free heavy metal ions in the washing agents themselves and in the washing solutions.
- the amount used as a complexing agent is advantageously 0.1 to 2% based on the total weight of the detergent components.
- bleach stabilization for example for sodium perborate
- detergents and in the bleaching of textiles, cellulose or paper raw materials Traces of heavy metals such as iron, copper and manganese occur in the washing powder itself, in the water and in the textile goods and catalyze the decomposition of the sodium perborate.
- the complexing agents mentioned bind these metal ions and prevent the undesired decomposition of the bleaching system during storage and in the wash liquor. This increases the efficiency of the bleaching system and fiber damage is suppressed.
- the complexing agents mentioned can be used as so-called preservatives, advantageously in an amount of 0.05 to 1% by weight, based on the total weight of the detergent formulation.
- the complexing agents mentioned prevent metal-catalyzed oxidative decomposition.
- They can be used to stabilize phosphates in alkaline degreasing baths and prevent the precipitation of lime soaps, thereby preventing "tarnishing" of non-ferrous surfaces and extending the service life of alkaline cleaning baths.
- the cooling water treatment with the complex images mentioned prevents deposits or dissolves existing ones. Use in an alkaline medium and thus the elimination of corrosion problems is an advantage.
- the complexing agents mentioned can be used in developer / fixing baths which are prepared with hard water in order to prevent the precipitation of poorly soluble calcium and magnesium salts.
- the precipitations lead to gray haze on films and images, as well as deposits in the tanks, which can thus advantageously be avoided.
- Iron III complexing agent solutions can advantageously be used in bleach-fix baths, where they can replace the hexacyanoferrate solutions, which are of ecological concern.
- applications in pharmaceuticals, cosmetics and foodstuffs are considered as various applications in order to prevent the metal-catalyzed oxidation of olefinic double bonds and thus the rancidity of the products.
- Cu, Fe, Mn, Zn complexes are used to remedy heavy metal deficits.
- the heavy metals are added as chelates to prevent precipitation as biologically inactive, insoluble salts.
- flue gas scrubbing namely the removal of NO x from flue gases
- H2S oxidation namely the removal of NO x from flue gases
- metal extraction namely the removal of metal oxides
- catalysts for org Use as catalysts for org.
- Syntheses e.g. air oxidation of paraffins, hydroformylation of olefins to alcohols.
- the complexing agents mentioned for alkaline earth and heavy metal ions are used as complexing agents in general and very particularly in detergents and cleaning agents and dishwashing detergents, in particular as complexing agents for heavy metal and / or alkaline earth metal ions, as bleach stabilizers and as builders.
- the compounds mentioned are generally used in washing and cleaning formulations in an amount of 0.01 to 20% by weight, preferably 0.05 to 10% by weight, based on the total weight of the washing-agent formulation.
- amounts from 1 to 10% by weight are preferred, when used as a bleach stabilizer for perborates, amounts from 0.05 to 1% by weight are particularly preferred.
- amounts of 0.1 to 2% by weight are preferred.
- Detergent and cleaning agent formulations which, based on the total weight, contain 0.01 to 20, preferably 0.05 to 10% by weight of the compound mentioned, as a rule contain, as additional constituents, 6 to 25% by weight, based on the total weight.
- % Surfactants 15 to 50% by weight builder and optionally co-builder, 5 to 35% by weight bleach and optionally bleach activators, 3 to 30% by weight auxiliaries such as enzymes, foam regulators, corrosion inhibitors, optical brighteners, fragrances, dyes, or Formulation aids, such as Sodium sulfate.
- the compounds mentioned can also be used in their properties as complexing agents, builders and bleach stabilizers in washing and cleaning formulations together with other agents of the prior art, the general properties with regard to sequestration, incrustation inhibition, primary washing action and bleaching action can possibly be significantly improved .
- aqueous formaldehyde solution 100 g (1 mol) of 30% strength by weight aqueous formaldehyde solution are initially introduced, and a solution of 52 g (0.5 mol) of serine in 250 g of water, in which: a pH of 8.5 was previously set with 37 g of 40% NaOH.
- aqueous solution of serine-N, N-diacetonitrile prepared under 1 is added dropwise to 102 g (1.02 mol) of 40% strength by weight aqueous sodium hydroxide solution at 95 to 110 ° C. in the course of 1 hour. After stirring for a further 3 hours at 100 ° C., no more ammonia development is found (total 0.94 mol).
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Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Serin-N,N-diessigsäure und Derivaten und das Zwischenprodukt Serin-N,N-diacetonitril für die Herstellung von Serin-N,N-diessigsäure und ihren Salzen.The invention relates to a process for the preparation of serine-N, N-diacetic acid and derivatives and the intermediate product serine-N, N-diacetonitrile for the production of serine-N, N-diacetic acid and its salts.
In einer Veröffentlichung von L. Erdey et al. in Acta Chim. Hung., Tomus 21, S. 327-332 (1959) werden die komplexbildenden Eigenschaften von 2,3-Dihydroxypropylamin-N,N-diessigsäure, Serin-N,N-diessigsäure, hergestellt aus D,L-Serin und Chloressigsäure, und L-Gutaminsäure-N,N-diessigsäure im Hinblick auf die Stabilität der mit Erdalkalimetallionen gebildeten Komplexe beschrieben.In a publication by L. Erdey et al. in Acta Chim. Hung., Tomus 21, pp. 327-332 (1959) describe the complexing properties of 2,3-dihydroxypropylamine-N, N-diacetic acid, serine-N, N-diacetic acid, made from D, L-serine and chloroacetic acid, and L-gutamic acid-N, N-diacetic acid with regard to the stability of the complexes formed with alkaline earth metal ions.
Aufgabe der vorliegenden Erfindung ist es, Komplexbildner für Erdalkali-und Schwermetallionen für die verschiedensten technischen Gebiete, insbesondere für Waschmittel, zur Verfügung zu stellen, die neben guten komplexbildenden Eigenschaften ökologisch unbedenklich, möglichst keinen Phosphor enthalten und biologisch gut abbaubar sind. Für diese Komplexbildner soll ein technisch vorteilhaftes Herstellverfahren entwickelt werden.The object of the present invention is to provide complexing agents for alkaline earth and heavy metal ions for a wide variety of technical fields, in particular for detergents, which, in addition to good complexing properties, are ecologically harmless, contain no phosphorus if possible and are readily biodegradable. A technically advantageous manufacturing process is to be developed for these complexing agents.
Es wurde gefunden, daß Serin-N,N-diessigsäure in Form der freien Säure oder insbesondere der Natrium-, Kalium-, Ammonium- oder organischen Aminsalze hervorragende Komplexbildner für Calcium-, Magnesium- sowie Eisen-, Kupfer-, Nickel- und Manganionen darstellen, während die Säurederivate, insbesondere Amide, Ester und die Nitrile bevorzugt Zwischenprodukte für die Herstellung der Säure und ihren Salzen sind.It has been found that serine-N, N-diacetic acid in the form of the free acid or in particular the sodium, potassium, ammonium or organic amine salts are excellent complexing agents for calcium, magnesium and iron, copper, nickel and manganese ions represent, while the acid derivatives, especially amides, esters and the nitriles are preferred intermediates for the preparation of the acid and its salts.
Gegenstand der Erfindung ist daher ein Verfahren zur Herstellung von Verbindungen der Formel I
in der Y für den Rest -COOH, der gegebenenfalls in Form eines Alkalimetall-, Ammonium- oder substituierten Ammoniumsalzes vorliegt, oder für den Rest -CN steht und
X eine Hydroxylgruppe, wobei die dadurch vorliegende Carbonsäuregruppe gegebenenfalls in Form eines Alkalimetall-, Ammonium- oder substituierten Ammoniumsalzes vorliegt, oder einen Rest -NR³R⁴, in dem R³ und R⁴ gleich oder verschiedenen sind und für ein Wasserstoffatom oder einen Alkylrest mit 1 bis 4 C-Atomen stehen,
bedeutet, indem man 1 Mol Serin (3-Hydroxy-2-aminopropionsäure) ggfs. in Form eines Alkalisalzes oder des Säureamids, ggfs. am Amidstickstoffatom durch ein oder zwei Alkylreste mit 1 bis 4 C-Atomen substituiert, in Wasser, einem organischen Lösungsmittel oder ihren Mischungen mit 2,0 bis 2,6 Mol Formaldehyd und 2,0 bis 2,3 Mol flüssigen Blausäure bei Temperaturen von 0 bis 45°C oder mit 2,0 bis 2,3 Mol Alkalicyanid bei Temperaturen von 40 bis 100°C umsetzt und ggfs. vorliegende Amid- und die Nitrilgruppen in Gegenwart von einer Säure oder Base hydrolysiert und ggfs. die freie Säure oder ein Salz gemäß Formel I isoliert.The invention therefore relates to a process for the preparation of compounds of the formula I.
in which Y represents the radical -COOH, which is optionally in the form of an alkali metal, ammonium or substituted ammonium salt, or represents the radical -CN and
X is a hydroxyl group, the carboxylic acid group thereby present optionally being in the form of an alkali metal, ammonium or substituted ammonium salt, or a radical -NR³R⁴, in which R³ and R⁴ are identical or different and represent a hydrogen atom or an alkyl radical with 1 to 4 C. -Atoms stand,
means by 1 mol of serine (3-hydroxy-2-aminopropionic acid), optionally in the form of an alkali salt or acid amide, optionally substituted on the amide nitrogen atom by one or two alkyl radicals having 1 to 4 carbon atoms, in water, an organic solvent or their mixtures with 2.0 to 2.6 mol of formaldehyde and 2.0 to 2.3 mol of liquid hydrocyanic acid at temperatures from 0 to 45 ° C. or with 2.0 to 2.3 mol of alkali metal cyanide at temperatures from 40 to 100 ° C and, if appropriate, hydrolyze the amide and nitrile groups present in the presence of an acid or base and, if appropriate, isolate the free acid or a salt of the formula I.
Im einzelnen sind zu nennen die freie Serin-N,N-diessigsäure und die Natrium-, Kalium- und Ammoniumsalze, insbesondere das Trinatrium-, Trikalium- und Triammoniumsalz, sowie organische Triaminsalze mit einem tertiären Stickstoffatom.The free serine N, N-diacetic acid and the sodium, potassium and ammonium salts, in particular the trisodium, tripotassium and triammonium salt, and organic triamine salts with a tertiary nitrogen atom are to be mentioned in particular.
Als den organischen Aminsalzen zugrundeliegende Basen kommen insbesondere tertiäre Amine, wie Trialkylamine mit 1 bis 4 C-Atomen im Alkyl, wie Trimethyl- und Triethylamin, und Trialkanolamine mit 2 oder 3 C-Atomen im Alkanolrest, bevorzugt Triethanolamin und Tripropanolamin, in Betracht.The bases on which the organic amine salts are based are, in particular, tertiary amines, such as trialkylamines having 1 to 4 carbon atoms in the alkyl, such as trimethyl and triethylamine, and trialkanolamines having 2 or 3 carbon atoms in the alkanol radical, preferably triethanolamine and tripropanolamine.
Die bevorzugte Ausgangsverbindung ist Serin in Form seines racemischen Gemisches und ggfs. in Form des Natrium-, Kalium- oder Ammoniumsalzes.The preferred starting compound is serine in the form of its racemic mixture and optionally in the form of the sodium, potassium or ammonium salt.
Die Umsetzung erfolgt in an sich üblicher Weise nach Art einer Strecker'schen Synthese, vgl. Houben-Weyl, Bd. 11/2, S. 408-412 (1958), Thieme-Verlag, Stuttgart.The implementation takes place in a conventional manner in the manner of a Strecker synthesis, cf. Houben-Weyl, Vol. 11/2, pp. 408-412 (1958), Thieme-Verlag, Stuttgart.
Als Lösemittel kommen vorzugsweise Wasser zum Einsatz, oder mit Wasser mischbare organische Lösemittel, wie Methanol, Ethanol, n-Propanol, iso-Propanol, tertiär-Butanol, Dioxan oder Tetrahydrofuran. Es können auch Mischungen dieser organischen Lösungsmittel untereinander oder ihre Mischungen mit Wasser verwendet werden. Bei wäßrigen Mischungen wird zweckmäßigerweise zum Gewicht des Wassers 10 bis 70 Gew.% organisches Lösungsmittel gegeben.Water is preferably used as the solvent, or organic solvents which are miscible with water, such as methanol, ethanol, n-propanol, isopropanol, tertiary butanol, dioxane or tetrahydrofuran. Mixtures of these organic solvents with one another or their mixtures with water can also be used. In the case of aqueous mixtures, 10 to 70% by weight of organic solvent is expediently added to the weight of the water.
Die Konzentration der Ausgangsverbindungen im jeweiligen Lösungsmittel beträgt vorteilhaft 10 bis 80 Gew.%, vorzugsweise 20 bis 70 Gew.%.The concentration of the starting compounds in the respective solvent is advantageously 10 to 80% by weight, preferably 20 to 70% by weight.
Bei einer zweckmäßigen und bevorzugten Reaktionsführung wird das Natrium- oder Kaliumsalz des Serins in einem der o.g. Lösungsmittel oder Lösungsmittelgemische, wobei eine wäßrige Lösung bevorzugt wird, mit dem Formaldehyd in Form seiner wäßrigen, ca. 30 gew.%igen Lösung und der flüssigen Blausäure bei den bevorzugten Temperaturen von 15 bis 25°C umgesetzt.In an expedient and preferred reaction procedure, the sodium or potassium salt of the serine in one of the abovementioned solvents or solvent mixtures, with an aqueous solution being preferred, with the formaldehyde in the form of its aqueous, about 30% by weight solution and the liquid hydrocyanic acid the preferred temperatures of 15 to 25 ° C implemented.
Die Umsetzung mit Akalicyanid, insbesondere Natrium- oder Kaliumcyanid, anstelle der flüssigen Blausäure erfolgt bevorzugt bei 70 bis 100°C.The reaction with akalicyanide, in particular sodium or potassium cyanide, is preferably carried out at 70 to 100 ° C. instead of the liquid hydrocyanic acid.
Für die Umsetzung mit flüssiger Blausäure kommen zweckmäßigerweise pH-Bereiche von 0 bis 11, vorzugsweise 3 bis 9, in Betracht, die entsprechend mit einer Säure oder Base eingestellt werden können.For the reaction with liquid hydrocyanic acid, pH ranges from 0 to 11, preferably 3 to 9, are expedient, which can be adjusted accordingly with an acid or base.
Das entstandene Zwischenprodukt Serin-N,N-diacetonitril ist in der Literatur noch nicht beschrieben.The resulting intermediate, serine-N, N-diacetonitrile, has not yet been described in the literature.
In der Regel schließt sich für die vorliegenden Nitrilgruppen und ggfs. vorhandenen Ester- oder Amidgruppen eine Hydrolyse oder Verseifung zur Carbonsäure in an sich üblicher Weise in einem wäßrigen Reaktionsgemisch ggfs. nach Zusatz von Wasser in Gegenwart von Alkalien, wie Natrium- oder Kaliumhydroxid, oder von Säure, wie Schwefel- oder Salzsäure, an.As a rule, for the nitrile groups present and any ester or amide groups present, hydrolysis or saponification to give the carboxylic acid is carried out in a conventional manner in an aqueous reaction mixture, if appropriate after adding water in the presence of alkalis, such as sodium or potassium hydroxide, or of acid such as sulfuric or hydrochloric acid.
Diese Hydrolyse wird zweckmäßigerweise bei Temperaturen von 20 bis 110°C, vorzugsweise 40 bis 100°C, durchgeführt, bei ggfs. geringem Überschuß an Base oder Säure.This hydrolysis is expediently carried out at temperatures from 20 to 110 ° C., preferably 40 to 100 ° C., with a slight excess of base or acid, if necessary.
Entsprechend den Reaktionsbedingungen wird bevorzugt die Serin-N,N-diessigsäure oder ein Alkalisalz erhalten. Anschließend können ohne weiteres Salze mit einem anderen Kation hergestellt werden.According to the reaction conditions, the serine-N, N-diacetic acid or an alkali salt is preferably obtained. Then salts with another cation can be prepared without further notice.
Falls erforderlich, kann auch umgekehrt aus der erhaltenen Säure in üblicher Weise ein Säurederivat hergestellt werden.If necessary, an acid derivative can also be produced in the usual way from the acid obtained.
Die Verbindungen der Formel I können ohne Schwierigkeiten in reiner Form isoliert werden. Für die freie Säure und die Salze bieten sich insbesondere Sprüh- oder Gefriertrocknung, Kristallisation oder Fällung an. Es kann vorteilhaft sein, die angefallene Lösung direkt einer technischen Verwendung zuzuführen.The compounds of formula I can be isolated in pure form without difficulty. Spray or freeze drying, crystallization or precipitation are particularly suitable for the free acid and the salts. It can be advantageous to use the resulting solution directly for technical use.
Das erfindungsgemäße Herstellungsverfahren hat gegenüber bekannten Verfahren insbesondere zur Herstellung von Serin-N,N-diessigsäure und ihren Salzen den Vorteil, daß praktisch keine anorganische Salzlast anfällt. Aufgrund der leichten Verfügbarkeit der Ausgangsverbindungen werden außerordentlich günstige großtechnische Verfahren zur Verfügung gestellt.The production process according to the invention has the advantage over known processes, in particular for the production of serine-N, N-diacetic acid and its salts, that there is practically no inorganic salt load. Due to the easy availability of the starting compounds, extremely inexpensive large-scale processes are made available.
Die durch die Erfindung hergestellte Serin-N,N-diessigsäure und ihre Salze sind in hervorragender Weise geeignet, Erdalkali- und Schwermetallionen, insbesondere Calcium-, Magnesium- sowie Eisen-, Kupfer-, Nickel- und Manganionen, zu komplexieren. Aufgrund dieser Fähigkeit weisen sie eine Vielzahl von technischen Anwendungsmöglichkeiten auf. Da es sich um biologisch sehr gut abbaubare Verbindungen handelt, können sie in großen Mengen überall dort eingesetzt werden, wo die Abwässer geklärt werden müssen und auch phosphorhaltige Verbindungen vermieden werden sollen.The serine-N, N-diacetic acid and its salts produced by the invention are outstandingly suitable for complexing alkaline earth and heavy metal ions, in particular calcium, magnesium as well as iron, copper, nickel and manganese ions. Because of this ability, they have one Variety of technical applications. Since they are biodegradable compounds, they can be used in large quantities wherever the waste water has to be clarified and phosphorus-containing compounds should also be avoided.
In Wasch- und Reinigungsmitteln können die genannten Komplexbildner eingesetzt werden, um den Gehalt an freien Schwermetallionen in den Waschmitteln selbst und in den Waschlösungen zu kontrollieren. Die Einsatzmenge als Komplexbildner beträgt zweckmäßigerweise 0,1 bis 2 % bezogen auf das Gesamtgewicht der Waschmittelbestandteile.The complexing agents mentioned can be used in washing and cleaning agents in order to control the content of free heavy metal ions in the washing agents themselves and in the washing solutions. The amount used as a complexing agent is advantageously 0.1 to 2% based on the total weight of the detergent components.
Ihre vorteilhafte Wirkung liegt auch in einer Bleichmittelstabilisierung, beispielsweise für Natriumperborat, in Waschmitteln und bei der Bleiche von Textilien, Zellstoff oder Papierrohstoff. Spuren von Schwermetallen wie Eisen, Kupfer und Mangan, kommen im Waschpulver selbst, im Wasser und im Textilgut vor und katalysieren die Zersetzung des Natriumperborates. Die genannten Komplexbildner binden diese Metallionen und verhindern die unerwünschte Zersetzung des Bleichsystems während der Lagerung und in der Waschflotte. Dadurch erhöht sich die Effizienz des Bleichsystems und Faserschädigungen werden zurückgedrängt.Their advantageous effect also lies in bleach stabilization, for example for sodium perborate, in detergents and in the bleaching of textiles, cellulose or paper raw materials. Traces of heavy metals such as iron, copper and manganese occur in the washing powder itself, in the water and in the textile goods and catalyze the decomposition of the sodium perborate. The complexing agents mentioned bind these metal ions and prevent the undesired decomposition of the bleaching system during storage and in the wash liquor. This increases the efficiency of the bleaching system and fiber damage is suppressed.
Zusätzlich werden Enzyme, opt. Aufheller und Duftstoffe vor schwermetallkatalysierter oxidativer Zersetzung geschützt.In addition, enzymes, opt. Brighteners and fragrances protected from heavy metal catalyzed oxidative decomposition.
In flüssigen Waschmittelformulierungen können die genannten Komplexbildner als sog. Konservierungsmittel, zweckmäßig in einer Menge von 0,05 bis 1 Gew.%, bezogen auf das Gesamtgewicht der Waschmittelformulierung, eingesetzt werden.In liquid detergent formulations, the complexing agents mentioned can be used as so-called preservatives, advantageously in an amount of 0.05 to 1% by weight, based on the total weight of the detergent formulation.
In Seifen verhindern die genannten Komplexbildner beispielsweise metallkatalysierte oxidative Zersetzungen.In soaps, for example, the complexing agents mentioned prevent metal-catalyzed oxidative decomposition.
Weiterhin dienen sie in hervorragender Weise in Wasch- und Reinigungsmitteln als Gerüststoff (Builder), um Ausfällungen und Inkrustationen auf dem Gewebe zu verhindern.Furthermore, they serve as an excellent builder in detergents and cleaning agents to prevent precipitation and incrustation on the fabric.
Sie können in vorteilhafter Weise überall dort eingesetzt werden, wo bei technischen Verfahren Ausfällungen von Ca-, Mg- und Schwermetallsalzen stören und verhindert werden sollen. Beispielsweise zur Verhinderung von Ablagerungen und Verkrustungen in Kesseln, Rohrleitungen, an Sprühdüsen oder allgemein an glatten Oberflächen.They can advantageously be used wherever the precipitation of calcium, magnesium and heavy metal salts is to be disrupted and prevented in technical processes. For example, to prevent deposits and incrustations in boilers, pipelines, on spray nozzles or generally on smooth surfaces.
Sie können zur Stabilisierung von Phosphaten in alkalischen Entfettungsbädern und Verhinderung der Ausfällung von Kalkseifen dienen und verhindern dadurch das "Anlaufen" von Nichteisenoberflächen und verlängern die Standzeiten von alkalischen Reinigerbädern.They can be used to stabilize phosphates in alkaline degreasing baths and prevent the precipitation of lime soaps, thereby preventing "tarnishing" of non-ferrous surfaces and extending the service life of alkaline cleaning baths.
Sie können als Komplexbildner in alkalischen Entrostungs- und Entzunderungsbädern verwendet werden sowie in galvanischen Bädern anstelle von Cyaniden, um Verunreinigungen zu maskieren.They can be used as complexing agents in alkaline rust removal and descaling baths as well as in galvanic baths instead of cyanides to mask impurities.
Die Kühlwasserbehandlung mit den genannten Komplexbildern verhindert Ablagerungen bzw. löst bereits vorhandene wieder auf. Von Vorteil ist die Anwendung in alkalischem Medium und damit die Beseitigung von Korrosionsproblemen.The cooling water treatment with the complex images mentioned prevents deposits or dissolves existing ones. Use in an alkaline medium and thus the elimination of corrosion problems is an advantage.
Bei der Polymerisation von Kautschuk können sie zur Herstellung der dabei verwendeten Redoxkatalysatoren verwendet werden. Sie verhindern zusätzlich das Ausfallen von Eisenhydroxid im alkalischen Polymerisationsmilieu.When polymerizing rubber, they can be used to produce the redox catalysts used. They also prevent the precipitation of iron hydroxide in the alkaline polymerization environment.
In der photographischen Industrie können die genannten Komplexbildner in Entwickler/Fixierbädern, die mit hartem Wasser angesetzt werden, verwendet werden, um die Ausfällung schwerlöslicher Ca- und Mg-salze zu verhindern. Die Ausfällungen führen zur Grauschleiern auf Filmen und Bildern sowie Ablagerungen in den Tanks, die somit vorteilhaft vermieden werden können. Eisen-III-Komplexbildnerlösungen können vorteilhaft in Bleichfixierbädern eingesetzt werden, wo sie die aus ökologischen Gründen bedenklichen Hexacyanoferratlösungen ersetzen können.In the photographic industry, the complexing agents mentioned can be used in developer / fixing baths which are prepared with hard water in order to prevent the precipitation of poorly soluble calcium and magnesium salts. The precipitations lead to gray haze on films and images, as well as deposits in the tanks, which can thus advantageously be avoided. Iron III complexing agent solutions can advantageously be used in bleach-fix baths, where they can replace the hexacyanoferrate solutions, which are of ecological concern.
In der Textilindustrie können sie zur Entfernung von Schwermetallspuren während des Herstellungs- bzw. Färbeprozesses von natürlichen und synthetischen Fasern dienen. Dadurch werden viele Störungen verhindert: Schmutzflecken und Streifen auf dem Textilgut, Verlust des Glanzes, schlechte Benetzbarkeit, unegale Färbungen und Farbfehler.In the textile industry, they can be used to remove traces of heavy metals during the manufacturing or dyeing process of natural and synthetic fibers. This prevents many faults: dirt stains and streaks on the textile, loss of gloss, poor wettability, uneven dyeing and color errors.
In der Papierindustrie können sie zur Eliminierung von Schwermetall/Eisenionen verwendet werden. Die Ablagerung von Eisen auf Papier führt zu "heißen Flecken", an denen die oxidative, katalytische Zerstörung der Zellulose beginnt.In the paper industry they can be used to eliminate heavy metal / iron ions. The deposition of iron on paper leads to "hot spots" where the oxidative, catalytic destruction of cellulose begins.
Als verschiedene Anwendungen kommen beispielsweise Anwendungen in Pharmazeutika, Kosmetika und Nahrungsmitteln in Betracht, um die metallkatalysierte Oxidation von olefinischen Doppelbindungen und damit das Ranzigwerden der Erzeugnisse zu verhindern.For example, applications in pharmaceuticals, cosmetics and foodstuffs are considered as various applications in order to prevent the metal-catalyzed oxidation of olefinic double bonds and thus the rancidity of the products.
In der Pflanzenernährung werden zur Behebung von Schwermetalldefiziten Cu, Fe, Mn, Zn-Komplexe verwendet. Die Schwermetalle werden als Chelate zugegeben, um die Ausfällung als biologisch inaktive, unlösliche Salze zu verhindern.In plant nutrition, Cu, Fe, Mn, Zn complexes are used to remedy heavy metal deficits. The heavy metals are added as chelates to prevent precipitation as biologically inactive, insoluble salts.
Weitere Anwendungsgebiete für die genannten Komplexbildner sind die Rauchgaswäsche, und zwar die Entfernung von NOx aus Rauchgasen, die H₂S-Oxidation, die Metallextraktion, sowie Anwendung als Katalysatoren für org. Synthesen (z.B. Luftoxidation von Paraffinen, Hydroformylierung von Olefinen zu Alkoholen).Other areas of application for the complexing agents mentioned are flue gas scrubbing, namely the removal of NO x from flue gases, H₂S oxidation, metal extraction, and use as catalysts for org. Syntheses (e.g. air oxidation of paraffins, hydroformylation of olefins to alcohols).
Die genannten Komplexbildner für Erdalkali- und Schwermetallionen werden als Komplexbildner allgemein und ganz besonders hervorzuheben in Wasch- und Reinigungsmitteln sowie Spül- und Waschhilfsmitteln, insbesondere als Komplexbildner für Schwermetall- und/oder Erdalkaliionen, als Bleichmittelstabilisatoren sowie als Gerüststoffe (Builder) verwendet.The complexing agents mentioned for alkaline earth and heavy metal ions are used as complexing agents in general and very particularly in detergents and cleaning agents and dishwashing detergents, in particular as complexing agents for heavy metal and / or alkaline earth metal ions, as bleach stabilizers and as builders.
Die genannten Verbindungen werden in Wasch- und Reinigungsformulierungen im allgemeinen in eine Menge von 0,01 bis 20 Gew.%, bevorzugt 0,05 bis 10 Gew.%, bezogen auf das Gesamtgewicht der Waschmittelformulierung, eingesetzt.The compounds mentioned are generally used in washing and cleaning formulations in an amount of 0.01 to 20% by weight, preferably 0.05 to 10% by weight, based on the total weight of the washing-agent formulation.
Bei einer Verwendung bevorzugt als Gerüststoff sind Mengen von 1 bis 10 Gew.%, bei einer Verwendung bevorzugt als Bleichmittelstabilisator für Perborate sind Mengen von 0,05 bis 1 Gew.% besonders bevorzugt. Bei einer Verwendung insbesondere als Komplexbildner in Waschmitteln sind Mengen von 0,1 bis 2 Gew.% bevorzugt.When used preferably as a builder, amounts from 1 to 10% by weight are preferred, when used as a bleach stabilizer for perborates, amounts from 0.05 to 1% by weight are particularly preferred. When used in particular as a complexing agent in detergents, amounts of 0.1 to 2% by weight are preferred.
Wasch- und Reinigungsmittelformulierungen, die, bezogen auf das Gesamtgewicht, 0,01 bis 20, bevorzugt 0,05 bis 10 Gew.%, genannte Verbindung enthalten, enthalten in der Regel als zusätzliche Bestandteile, bezogen auf das Gesamtgewicht, 6 bis 25 Gew.% Tenside, 15 bis 50 Gew.% Builder und gegebenenfalls Co-Builder, 5 bis 35 Gew.% Bleichmittel und gegebenenfalls Bleichmittelaktivatoren, 3 bis 30 Gew.% Hilfsstoffe, wie Enzyme, Schaumregulatoren, Korrosionsinhibitoren, optische Aufheller, Duftstoffe, Farbstoffe, oder Formulierhilfsmittel, wie z.B. Natriumsulfat.Detergent and cleaning agent formulations which, based on the total weight, contain 0.01 to 20, preferably 0.05 to 10% by weight of the compound mentioned, as a rule contain, as additional constituents, 6 to 25% by weight, based on the total weight. % Surfactants, 15 to 50% by weight builder and optionally co-builder, 5 to 35% by weight bleach and optionally bleach activators, 3 to 30% by weight auxiliaries such as enzymes, foam regulators, corrosion inhibitors, optical brighteners, fragrances, dyes, or Formulation aids, such as Sodium sulfate.
Die genannten Verbindungen können in ihrer Eigenschaft als Komplexbildner, Gerüststoffe und Bleichmittelstabilisatoren auch verwendet werden in Wasch- und Reinigungsformulierungen zusammen mit anderen Mitteln des Standes der Technik, wobei die allgemeinen Eigenschaften im Hinblick auf Sequestrierung, Inkrustationsinhibierung, Primärwaschwirkung und Bleichwirkung unter Umständen deutlich verbessert werden können.The compounds mentioned can also be used in their properties as complexing agents, builders and bleach stabilizers in washing and cleaning formulations together with other agents of the prior art, the general properties with regard to sequestration, incrustation inhibition, primary washing action and bleaching action can possibly be significantly improved .
Man legt 100 g (1 mol) 30 gew.%ige wäßrige Formaldehydlösung vor und tropft innerhalb von 1,25 Stunden bei 20 bis 25°C eine Lösung von 52 g (0,5 mol) Serin in 250 g Wasser zu, bei welcher zuvor mit 37 g 40 %iger NaOH ein pH-Wert von 8,5 eingestellt wurde.100 g (1 mol) of 30% strength by weight aqueous formaldehyde solution are initially introduced, and a solution of 52 g (0.5 mol) of serine in 250 g of water, in which: a pH of 8.5 was previously set with 37 g of 40% NaOH.
Nach 30-minütigem Weiterrühren bei 25°C werden bei 15 bis 20°C 27 g (1 mol) Blausäure innerhalb von 1,5 Stunden zugetropft. Anschließend wird bei 20°C 30 Minuten weitergerührt, bis Ausgangsmaterialien nicht mehr nachweisbar sind und vollständige Umsetzung erreicht ist.After stirring for a further 30 minutes at 25 ° C., 27 g (1 mol) of hydrocyanic acid are added dropwise at 15 to 20 ° C. in the course of 1.5 hours. The mixture is then stirred at 20 ° C for 30 minutes until starting materials are no longer detectable and complete conversion is achieved.
Es werden 455 g einer ca. 20 %igen Lösung von Serin-N,N-diacetonitril (=̂ 98 % d.Th.) erhalten. Die durch Gefriertrocknung isolierte Verbindung hat keinen scharfen Schmp. und schmilzt unter Zersetzung.
Analyse:
C₇H₉N₃O₃ (183.16) ber. C 45,90 % H 4,95 % N 22,94 % O 26,21 %
gef. C 45,43 % H 5,08 % N 22,72 % O 26,76 %455 g of an approximately 20% solution of serine-N, N-diacetonitrile (= ̂ 98% of theory) are obtained. The compound isolated by freeze-drying has no sharp melting point and melts under decomposition.
Analysis:
C₇H₉N₃O₃ (183.16) calc. C 45.90% H 4.95% N 22.94% O 26.21%
found C 45.43% H 5.08% N 22.72% O 26.76%
Zu 102 g (1,02 mol) 40 gew.%ige wäßrige Natronlauge wird die unter 1 hergestellte wäßrige Lösung von Serin-N,N-diacetonitril innerhalb von 1 Stunde bei 95 bis 110°C zugetropft. Nach 3-stündigem Weiterrühren bei 100°C wird keine Ammoniakentwicklung mehr festgestellt (insgesamt 0,94 mol).The aqueous solution of serine-N, N-diacetonitrile prepared under 1 is added dropwise to 102 g (1.02 mol) of 40% strength by weight aqueous sodium hydroxide solution at 95 to 110 ° C. in the course of 1 hour. After stirring for a further 3 hours at 100 ° C., no more ammonia development is found (total 0.94 mol).
Es resultiert eine klare, gelbe, ca., 30 gew.%ige wäßrige Lösung von Serin-N,N-di-essigsäure-trinatriumsalz. (Auswaage: 390 g (=̂ 94 % d.Th.). Der Schmp. des isolierten Salzes liegt über 300°C.The result is a clear, yellow, approx., 30% by weight aqueous solution of trisodium salt of serine-N, N-di-acetic acid. (Weight: 390 g (= ̂ 94% of theory). The melting point of the isolated salt is above 300 ° C.
Die unter B hergestellte wäßrige Lösung von Serin-N,N-di-essigsäure-trinatriumsalz wird unter vermindertem Druck (Wasserstrahlpumpe) auf ca. 50 Gew.% aufkonzentriert. Mit konzentrierter Salzsäure wird ein pH-Wert von 2 eingestellt. Die Lösung tropft man anschließend auf die 4fache Volumenmenge Methanol. Der ausgefallene farblose Niederschlag wird abfiltriert und nochmals mit Methanol gewaschen. Nach dem Trocknen verbleiben 98 g (=̂ 86 % d.Th.) Serin-N,N-diessigsäure vom Schmp. 171 bis 173°C, vgl. s. Korman et al., J. Biol. Chem. 221, S. 116 (1956).The aqueous solution of serine-N, N-di-acetic acid trisodium salt produced under B is concentrated to about 50% by weight under reduced pressure (water jet pump). A pH of 2 is set with concentrated hydrochloric acid. The solution is then added dropwise to 4 times the volume of methanol. The colorless precipitate which has separated out is filtered off and washed again with methanol. After drying, 98 g (= ̂ 86% of theory) of serine-N, N-diacetic acid of mp. 171 to 173 ° C remain, cf. s. Korman et al., J. Biol. Chem. 221, p. 116 (1956).
Claims (2)
- A process for preparing a compound of the formula I
X is a hydroxyl group, in which case the resulting carboxylic acid group may be present in the form of an alkali metal, ammonium or substituted ammonium salt, or a radical -NR³R⁴, where R³ and R⁴ are identical or different and each is hydrogen or alkyl of from 1 to 4 carbon atoms, which comprises reacting 1 mol of serine, optionally in the form of an alkali metal salt, or of the acid amide, optionally monosubstituted or disubstituted on the amide nitrogen atom by alkyl of from 1 to 4 carbon atoms, in water, an organic solvent or a mixture thereof with from 2 to 2.6 mol of formaldehyde and from 2 to 2.3 mol of liquid hydrocyanic acid at from 0 to 45°C or with from 2 to 2.3 mol of an alkali metal cyanide at from 40 to 100°C, hydrolyzing any amide and the nitrile groups present in the presence of an acid or base, and as required isolating the free acid or a salt conforming to the formula I. - Serine-N,N-diacetonitrile as intermediate for preparing serine-N,N-diacetic acid and salts thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT88105376T ATE72229T1 (en) | 1987-04-11 | 1988-04-02 | PROCESS FOR THE PRODUCTION OF SERIN-N,NDIESIGS|URE AND DERIVATIVES. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3712329 | 1987-04-11 | ||
| DE19873712329 DE3712329A1 (en) | 1987-04-11 | 1987-04-11 | METHOD FOR THE PRODUCTION OF SERINE-N, N-DIACETIC ACID AND DERIVATIVES, THEIR USE, IN PARTICULAR AS COMPLEXING AGENTS, AND DETERGENT AND CLEANING AGENT THEREOF |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0287885A1 EP0287885A1 (en) | 1988-10-26 |
| EP0287885B1 true EP0287885B1 (en) | 1992-01-29 |
Family
ID=6325429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88105376A Expired - Lifetime EP0287885B1 (en) | 1987-04-11 | 1988-04-02 | Process for the preparation of serine-n,n-diacetic acid and its derivatives |
Country Status (8)
| Country | Link |
|---|---|
| US (2) | US4973730A (en) |
| EP (1) | EP0287885B1 (en) |
| JP (1) | JPS63267751A (en) |
| AT (1) | ATE72229T1 (en) |
| AU (1) | AU608592B2 (en) |
| CA (1) | CA1313673C (en) |
| DE (2) | DE3712329A1 (en) |
| ES (1) | ES2028924T3 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1213029B (en) * | 1986-01-30 | 1989-12-07 | Bracco Ind Chimica Spa | PARAMAGNETIC METAL ION CHELATES. |
| DE3829829A1 (en) * | 1988-09-02 | 1990-03-22 | Basf Ag | METHOD FOR PRODUCING THE TRINATRIUM SALT OF ISOSERIN-N, N-DIACETIC ACID |
| DE3901613A1 (en) * | 1989-01-20 | 1990-08-16 | Basf Ag | GLYCERINAMINOCARBOXYLATE, THEIR PRODUCTION AND USE |
| DE3914980A1 (en) * | 1989-05-06 | 1990-12-06 | Basf Ag | 2-METHYL AND 2-HYDROXYMETHYL-SERIN-N, N-DIESETIC ACID AND THEIR DERIVATIVES |
| US5362412A (en) * | 1991-04-17 | 1994-11-08 | Hampshire Chemical Corp. | Biodegradable bleach stabilizers for detergents |
| US5254290A (en) * | 1991-04-25 | 1993-10-19 | Genevieve Blandiaux | Hard surface cleaner |
| US5221496A (en) * | 1992-06-02 | 1993-06-22 | Basf Corp. | Aqueous prewash stain remover compositions with efficacy on tenacious oily stains |
| US5186856A (en) * | 1992-06-02 | 1993-02-16 | Basf Corp. | Aqueous prewash stain remover compositions with efficacy on tenacious oily stains |
| WO1994012606A1 (en) * | 1992-12-03 | 1994-06-09 | Basf Aktiengesellschaft | Iminodiacetic acid derivates used in cleaning compositions for the beverage and food industry, and for hard metallic, plastic, lacquered or glass surfaces |
| WO1994026691A1 (en) * | 1993-05-19 | 1994-11-24 | Akzo Nobel N.V. | (2-carboxy-3-hydroxy-propyl)-iminodiacetic acid and derivatives |
| DE4319935A1 (en) * | 1993-06-16 | 1994-12-22 | Basf Ag | Use of glycine-N, N-diacetic acid derivatives as complexing agents for alkaline earth and heavy metal ions |
| JP2983063B2 (en) * | 1994-10-07 | 1999-11-29 | エカ ケミカルズ アクチェボラーグ | bleach |
| CZ285638B6 (en) * | 1994-10-07 | 1999-10-13 | Eka Chemicals Ab | Particles containing peroxo-compound and agent containing thereof |
| US6034048A (en) * | 1995-03-01 | 2000-03-07 | Charvid Limited Liability Co. | Non-caustic cleaning composition using an alkali salt |
| US6194367B1 (en) * | 1995-03-01 | 2001-02-27 | Charvid Limited Liability Co. | Non-caustic cleaning composition comprising peroxygen compound and specific silicate and method of making the same in free-flowing, particulate form |
| US5663132A (en) * | 1995-03-01 | 1997-09-02 | Charvid Limited Liability Company | Non-caustic composition comprising peroxygen compound and metasilicate and cleaning methods for using same |
| US5488130A (en) * | 1995-03-31 | 1996-01-30 | The Dow Chemical Company | Amino nitrile intermediate for the preparation of 2-hydroxypropyl iminodiacetic acid |
| US5481018A (en) * | 1995-03-31 | 1996-01-02 | The Dow Chemical Company | Amino nitrile intermediate for the preparation of alanine diacetic acid |
| DE19518986A1 (en) * | 1995-05-29 | 1996-12-05 | Basf Ag | Process for the preparation of glycine-N, N-diacetic acid derivatives by reacting glycine derivatives or their precursors with formaldehyde and hydrogen cyanide or iminodiacetonitrile or imindodiacetic acid with corresponding aldehydes and hydrogen cyanide in an aqueous acidic medium |
| DE19518987A1 (en) * | 1995-05-29 | 1996-12-05 | Basf Ag | Process for the preparation of glycine-N, N-diacetic acid derivatives by reacting glycine derivatives or their precursors with formaldehyde and alkali metal cyanide in an aqueous alkaline medium |
| EP0783034B1 (en) * | 1995-12-22 | 2010-08-18 | Mitsubishi Rayon Co., Ltd. | Chelating agent and detergent comprising the same |
| JPH10168485A (en) * | 1996-12-13 | 1998-06-23 | Kao Corp | High-density detergent composition |
| TR199903221T2 (en) * | 1997-06-24 | 2000-08-21 | Unilever N.V. | Additive for a detergent formulation, a detergent formulation containing such an additive and the use of said formulation for cleaning bottles. |
| JP3290382B2 (en) | 1997-07-18 | 2002-06-10 | 花王株式会社 | Powder detergent composition |
| JPH11217590A (en) * | 1998-02-04 | 1999-08-10 | Kao Corp | Breaching and detergent composition |
| JP2000008099A (en) * | 1998-06-23 | 2000-01-11 | Kao Corp | Liquid detergent composition |
| JP2000008081A (en) * | 1998-06-25 | 2000-01-11 | Kao Corp | Detergent composition |
| CN1267972C (en) * | 2000-03-21 | 2006-08-02 | 和光纯药工业株式会社 | Semiconductor wafer cleaning agent and cleaning method |
| US20100056404A1 (en) * | 2008-08-29 | 2010-03-04 | Micro Pure Solutions, Llc | Method for treating hydrogen sulfide-containing fluids |
| CA2917252A1 (en) * | 2013-07-16 | 2015-01-22 | Axel Carstens | New salts, crystals, complexes, and derivatives of threonine diacetic acid, a process to prepare threonine diacetic acid, and the use thereof |
| RU2712767C2 (en) * | 2015-03-11 | 2020-01-31 | Басф Се | Mixture of chelating agents and method of producing said mixtures |
| US10519097B2 (en) | 2015-05-13 | 2019-12-31 | Basf Se | Process for making mixtures of chelating agents |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2500019A (en) * | 1946-10-08 | 1950-03-07 | Frederick C Bersworth | Method of producing polycarboxylic amino acids |
| US2786869A (en) * | 1954-06-16 | 1957-03-26 | Rohm & Haas | Nu-trialkylcarbinyl-nu-(hydroxyethyl-polyoxyethyl) glycines |
| US2781391A (en) * | 1956-03-06 | 1957-02-12 | Hans S Mannheimer | Detergent sulphonic acid and sulphate salts of certain amphoteric detergents |
| IT579083A (en) * | 1956-10-25 | |||
| NL243269A (en) * | 1958-09-12 | |||
| US3056799A (en) * | 1959-07-20 | 1962-10-02 | Sterling Drug Inc | Processes and intermediate products |
| US3424783A (en) * | 1966-05-06 | 1969-01-28 | Grace W R & Co | Aminonitrile synthesis |
| US3580950A (en) * | 1967-11-01 | 1971-05-25 | Frederick C Bersworth | Chelating compositions based on chelating acids and amines |
| BE759533A (en) * | 1969-11-28 | 1971-04-30 | Colgate Palmolive Co | DETERGENT COMPOSITIONS AND METHOD OF PREPARATION |
| BE792181A (en) * | 1971-12-02 | 1973-06-01 | Hoffmann La Roche | CITRIC ACID DERIVATIVES |
| US3864378A (en) * | 1973-02-05 | 1975-02-04 | Bethlehem Steel Corp | Process for preparing 2-hydroxyethyliminodiacetonitrile |
| DE2503582C3 (en) * | 1975-01-29 | 1979-10-04 | Basf Ag, 6700 Ludwigshafen | Process for the preparation of N-alkylglycine nitriles |
| DE2555769C3 (en) * | 1975-12-11 | 1980-01-03 | Basf Ag, 6700 Ludwigshafen | Process for the preparation of glycine nitriles which are aliphatically substituted on the amino group |
| DE3712330A1 (en) * | 1987-04-11 | 1988-10-20 | Basf Ag | 2-HYDROXY-3-AMINO-PROPIONIC ACID-N, N-DIACETIC ACID AND THEIR DERIVATIVES, THEIR PRODUCTION AND USE, IN PARTICULAR AS A COMPLEXING AGENT AND THE DETERGENT AND CLEANING AGENT CONTAINING THEM |
| DE3829829A1 (en) * | 1988-09-02 | 1990-03-22 | Basf Ag | METHOD FOR PRODUCING THE TRINATRIUM SALT OF ISOSERIN-N, N-DIACETIC ACID |
-
1987
- 1987-04-11 DE DE19873712329 patent/DE3712329A1/en not_active Withdrawn
-
1988
- 1988-04-02 EP EP88105376A patent/EP0287885B1/en not_active Expired - Lifetime
- 1988-04-02 AT AT88105376T patent/ATE72229T1/en not_active IP Right Cessation
- 1988-04-02 DE DE8888105376T patent/DE3868118D1/en not_active Expired - Lifetime
- 1988-04-02 ES ES198888105376T patent/ES2028924T3/en not_active Expired - Lifetime
- 1988-04-04 US US07/177,366 patent/US4973730A/en not_active Expired - Fee Related
- 1988-04-07 CA CA000563543A patent/CA1313673C/en not_active Expired - Fee Related
- 1988-04-08 JP JP63085495A patent/JPS63267751A/en active Pending
- 1988-04-11 AU AU14463/88A patent/AU608592B2/en not_active Ceased
-
1990
- 1990-08-07 US US07/563,326 patent/US5019296A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE3712329A1 (en) | 1988-10-20 |
| US4973730A (en) | 1990-11-27 |
| US5019296A (en) | 1991-05-28 |
| DE3868118D1 (en) | 1992-03-12 |
| EP0287885A1 (en) | 1988-10-26 |
| AU1446388A (en) | 1988-10-13 |
| CA1313673C (en) | 1993-02-16 |
| JPS63267751A (en) | 1988-11-04 |
| ES2028924T3 (en) | 1992-07-16 |
| AU608592B2 (en) | 1991-04-11 |
| ATE72229T1 (en) | 1992-02-15 |
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