CA2305282A1 - Method for purifying 4-amino-piperidines - Google Patents
Method for purifying 4-amino-piperidines Download PDFInfo
- Publication number
- CA2305282A1 CA2305282A1 CA002305282A CA2305282A CA2305282A1 CA 2305282 A1 CA2305282 A1 CA 2305282A1 CA 002305282 A CA002305282 A CA 002305282A CA 2305282 A CA2305282 A CA 2305282A CA 2305282 A1 CA2305282 A1 CA 2305282A1
- Authority
- CA
- Canada
- Prior art keywords
- amino
- purifying
- reaction
- piperidines
- hydrogenation
- 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.)
- Abandoned
Links
- BCIIMDOZSUCSEN-UHFFFAOYSA-N piperidin-4-amine Chemical class NC1CCNCC1 BCIIMDOZSUCSEN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 238000004821 distillation Methods 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- VRJHQPZVIGNGMX-UHFFFAOYSA-N 4-piperidinone Chemical class O=C1CCNCC1 VRJHQPZVIGNGMX-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 2,2,6,6-tetrasubstituted 4-amino-piperidines Chemical class 0.000 claims abstract description 7
- 239000011541 reaction mixture Substances 0.000 claims abstract description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 230000000887 hydrating effect Effects 0.000 abstract 1
- 241001550224 Apha Species 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- JWUXJYZVKZKLTJ-UHFFFAOYSA-N Triacetonamine Chemical compound CC1(C)CC(=O)CC(C)(C)N1 JWUXJYZVKZKLTJ-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000002845 discoloration Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002638 heterogeneous catalyst Substances 0.000 description 4
- FTVFPPFZRRKJIH-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-amine Chemical compound CC1(C)CC(N)CC(C)(C)N1 FTVFPPFZRRKJIH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001414 amino alcohols Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000003053 piperidines Chemical class 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VDVUCLWJZJHFAV-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1 VDVUCLWJZJHFAV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D211/56—Nitrogen atoms
- C07D211/58—Nitrogen atoms attached in position 4
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D211/40—Oxygen atoms
- C07D211/44—Oxygen atoms attached in position 4
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Hydrogenated Pyridines (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for purifying 2,2,6,6-tetrasubstituted 4-amino-piperidines produced from the corresponding piperidin-4-ones, and subsequent distillation. According to the invention, the distilled 2,2,6,6-tetrasubstituted 4-amino-piperidine is reacted with hydrogen in the presence of a hydrating or dehydrating catalyst and the 4-amino piperidine is then separated from the reaction mixture.
Description
The present invention relates to a process for purifying 2,2,6,6-tetrasubstituted 4-aminopiperidines which have been prepared from the corresponding piperidin-4-ones with subsequent distillation.
In particular, the invention relates to a process for purifying 4-aminopiperidines of the formula I
I, R1 N~ R3 where R1 to R4 are C1-C6-alkyl, R1 and R2 and/or R3 and R4 together form a CHZ chain having from 2 to 5 carbon atoms, which have been prepared from the corresponding piperidin-4-ones of the formula II
II, R1 N~ R3 where the radicals R are as defined above, with subsequent distillation.
The 4-aminopiperidines which, owing to 2,2,6,6-substitution, eg.
tetraalkyl substitution, are designated as sterically hindered, are used in a variety of applications. In particular, they serve as intermediates in the preparation of UV stabilizers for synthetic polymers (see, for example: R. Gachter, H. Miiller (editors): Taschenbuch der Kunststoffadditive, Carl Hanser Verlag, Munich, 1979; F. Gugumus, Polym. Degrad. Stabil. 44 (1994), 299 - 322) and as chain regulators and stabilizers in the 30 preparation of polyamides (cf., for example: w0 952 84 43, DE-A-4 413 177).
0050/48395 CA o23os2s2 2000-o3-2s _ 2 It is of particular importance that the sterically hindered 4-aminopiperidines have not only a high chemical purity but also no or very little intrinsic color and that no discoloration takes place over a storage time of a number of months. This applies particularly when the 4-aminopiperidine is used for the preparation of stabilizers or employed directly as additive, since the product quality of these and thus also the quality of the stabilized polymers depends decisively on the chemical purity and, in particular, the color quality.
The sterically hindered 4-aminopiperidines are generally prepared industrially from dialkyl ketones, eg. acetone or acetone derivatives. The piperidines I can be obtained in a single step from the compounds by a catalytic ring-closure reaction in the presence of ammonia and hydrogen (DE-A-2 412 750) or from piperidin-4-ones II
O
II, R1 N~ R3 by aminative hydrogenation in one or two stages, for example catalytically. (See, for example DE-A-35 25 387, DE-A-2 040 975, DE-A-2 349 962, DE-A-26 21 870, EP-A-33 529, EP-A-42 119, Ep-A-303 279, EP-A-410 970, EP-A-611 137, EP-A-623 585 and DE-A-42 10 311).
The sterically hindered 4-aminopiperidines produced industrially are generally purified by distillation. (See, for example EP-A-33 529).
However, troublesome amounts of substances which give a color are still present, or are formed after a short time, in the 4-amino-2,2,6,6-tetraalkylpiperidines which are prepared using conventional processes.
0050/48395 Ca o23o52s2 2000-o3-2s According to DE-A-195 55 58, EP-A-28 555, US 3 819 710 and JP
01,160,947 CChem. Abstr. 111: 232081r), color-producing compounds in certain aminoalcohols, which compounds are formed in the preparation of the aminoalcohols from ethylene oxide and an appropriate amine, can be converted into less color-producing compounds by catalytic hydrogenation.
JP 06 25,410 CChem. Abstr. 12I: 56988n), JP-OS 48-52708 CChem.
Abstr. 80: 36697y), JP 05,345,821 CChem. Abstr. 120: 272327t), US
5 362 914 and EP-A-262 562 disclose that discolorations in certain polyamines can be reduced by treatment with hydrogen in the presence of hydrogenation catalysts.
DE-A-22 05 958 discloses a process for purifying tertiary amines which have been obtained by reacting primary alcohols with ammonia, by hydrogenation of the impurities before the final distillation of the tertiary amine.
The abovementioned compounds are different classes of substances from those of the sterically hindered 4-amino-piperidines of the present invention. Furthermore, the origin of the color producing impurities in the abovementioned compounds lies in the specific preparative processes and starting materials employed in each case.
Japanese Patent Application JP-OS 02-311 457 describes the purification of 2,2,6,6-tetraalkyl-4-piperidinones by treatment with hydrogen in the presence of a hydrogenation catalyst.
According to the examples given in this application, the process product (triacetoneamine, TAA) is so color-unstable that it has a much poorer color quality than the starting material after just one week's storage at 60°C.
The development of preparative methods for chemically pure sterically hindered 4-aminopiperidines having low discoloration has taken a completely different route:
DD-A-266 799 teaches reacting 4-amino-2,2,6,6-tetramethyl-piperidine in acetone/water solution with C02, separating off the precipitate, washing with acetone, subsequently decomposing thermally and purifying the product by distillation.
SU 18 11 527 describes a different purification process for sterically hindered 4-aminopiperidines I. In that process, the contaminated crude product is dissolved in an aprotic solvent, 0050/48395 CA o23os2s2 2000-o3-2s reacted with ethylene glycol, the reaction product is isolated, the 4-aminopiperidine is set free using aqueous alkali and is, after removal of the aqueous phase, fractionally distilled.
Both processes are extraordinarily complicated and costly.
Finally, the earlier German Application No. 19622269.9 describes a distillation process for purifying crude 4-amino-piperidines I
by' in a first step, removing high-boiling substances and possibly water from the crude piperidines by distillation, in a second step adding from 0.01 to 5~ by weight, based on the product of the first step, of a reducing agent, for example sodium borohydride, and, in a third step, isolating the plperidines I by distillation.
It is an object of the present invention to provide an inexpensive process which is simple to carry out and by means of which colorless, color-stable and highly pure sterically hindered 4-aminopiperidines, eg. of the formula I, can be made available.
This means products whose very low intrinsic coloration is maintained for a prolonged period and which have, at the same time, a low by-product content and contain no stabilizing auxiliaries. The reference to the 4-aminopiperidines I as "colorless" includes a minimum discoloration, namely up to a color number of at most 40 APHA (measured in accordance with DIN-ISO 6271).
We have found that this object is achieved by a process for purifying 2,2,6,6-tetrasubstituted 4-aminopiperidines which have been prepared from the corresponding piperidin-4-ones with subsequent distillation, which comprises reacting the distilled 2,2,6,6-tetrasubstituted 4-aminopiperidine with hydrogen in the presence of a hydrogenation or dehydrogenation catalyst and then again separating the 4-aminopiperidine from the reaction mixture.
In the sterically hindered 4-aminopiperidines I, the radicals R1, RZ, R3 and R4, independently of one another, are preferably C1-C3-alkyl, for example ethyl or methyl, in particular methyl.
The pure but discolored and/or color-unstable 4-amino-piperidine, eg. of the formula I, which has been obtained according to known methods by reaction of the corresponding piperidin-4-one, for example by aminative hydrogenation, and subsequent fractional rectification, is, according to the present invention, reacted with hydrogen in the presence of a hydrogenation catalyst, for example at from 20 to 200~C. Higher temperatures are also 0050/48395 ca o23os2s2 2000-o3-2s possible. Preference is given to a reaction temperature in the range from 50 to 150~C.
The reaction of the 4-aminopiperidine with hydrogen can be 5 carried out at atmospheric pressure or preferably under superatmospheric pressure, for example from 0.1 to 50 MPa. Higher pressures are also possible. Preference is given to a reaction pressure of from 1 to 30 MPa, in particular from 1 to 20 MPa.
The reaction of the 4-aminopiperidine with hydrogen can be carried out in the presence of a solvent or a solvent mixture which is inert under the reaction conditions, or preferably in the absence of solvent. When using a solvent, for example tetrahydrofuran, dioxane, 1,2-dimethoxyethane, methanol or ethanol, the reaction conditions are selected such that the solvent is present in liquid form in the reaction mixture.
As regards the hydrogenation catalysts which can be used, there are no restrictions. Dehydrogenation catalysts can also be used.
Suitable hydrogenation catalysts are, for example, catalysts which comprise copper, silver, gold, iron, cobalt, nickel, ruthenium, rhodium, palladium, rhenium, osmium, iridium, platinum, chromium, molybdenum or a mixture thereof.
The hydrogenation catalyst used can be homogeneously dissolved in the 4-aminopiperidine or in the mixture of 4-aminopiperidine and solvent, for example when using tris(triphenylphosphine)rhodium chloride, or, particularly preferably, be present in undissolved form, ie. heterogeneous.
Suitable heterogeneous catalysts are support-free catalysts such as Raney nickel or Raney cobalt, with the latter being present as a suspension in the reaction mixture, or supported catalysts which are preferably arranged as a fixed bed in the reactor. In the case of the supported catalysts, suitable support materials for the catalytically active metals or metal compounds are, for example, carbon, aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide, zinc oxide, magnesium oxide, silicon carbide, zeolites or mixtures thereof.
Examples which may be mentioned are supported catalysts comprising copper and/or cobalt and/or nickel and aluminum oxide and/or zirconium dioxide.
0050/48395 ca o23os2s2 2000-o3-2s For example, the two supported catalysts having the following compositions can be employed:
76% by weight of A1, calculated as A1203, 4% by weight of Cu, calculated as CuO, 10% by weight of Co, calculated as CoO, and 10% by weight of Ni, calculated as Ni0 (as described in DE-A-1 953 263) °r 31.5% by weight of Zr, calculated as Zr02, 50% by weight of Ni, calculated as NiO, 17% by weight of Cu, calculated as CuO, and 1.5% of Mo, calculated as Mo03 (as described in EP-A-696 572).
The necessary residence time of the 4-aminopiperidine over the catalyst is determined, inter alia, by the degree of discoloration of the distilled 4-aminopiperidine and by the desired decolorization and/or color stability of the piperidine.
As a rule, the residence time is longer, the higher the degree of discoloration of the 4-aminopiperidine used in the process step of the present invention and the higher the color quality requirements for the product.
Depending on the reaction conditions selected, residence times of from 10 minutes to a few hours are generally sufficient.
The process step of the present invention can be carried out either continuously, for example in tube reactors, stirred vessels or cascades of stirred vessels, or batchwise, for example in stirred vessels.
After carrying out the process step of the present invention, the 4-aminopiperidine is separated from the hydrogenation catalyst and from any solvent used.
Hydrogenation catalysts dissolved in the reaction product are separated off by distillation, with any solvent used and the 4-aminopiperidine being taken off in succession at the top in a customary manner.
Hydrogenation catalysts used in suspension are separated off by decantation and/or filtration. The reaction product can subsequently be distilled, which is in any case necessary if a solvent is used.
0050/48395 Ca o23o52s2 2000-o3-2s When using a hydrogenation catalyst arranged as a fixed bed, the reaction product is advantageously filtered in order to remove any abraded catalyst present. The reaction product can subsequently be distilled, which is in any case necessary if a solvent is used.
The process of the present invention gives, in a simple, inexpensive manner, pure sterically hindered 4-aminopiperidines which have virtually no intrinsic color and remain color-stable on storage, so that the addition of stabilizers is superfluous.
Examples The color of the sterically hindered 4-aminopiperidines was determined by measuring the APHA color number in accordance with DIN-ISO 6271.
In all examples, the storage of the TAD samples was carried out under comparable conditions (room temperature, in the dark).
Example 1 (Comparative Example):
1.632 kg of crude synthetic product having the composition (in %
by weight) 85.6% of 4-amino-2,2,6,6-tetramethylpiperidine (triacetonediamine, TAD) 9.0% of Hz0 about 0.7% of NH3 1.4% of 4-hydroxy-2,2,6,6-tetramethylpiperidine (triacetoneaminoalcohol,TAA-ol) 3.3% of by-products including high boilers, which had been obtained by aminative hydrogenation of 2,2,6,6-tetramethylpiperidin-4-one (triacetoneamine, TAA) [GC
purity: 99%; APHA color number: about 370 (measured as a 1%
strength solution in ethanol)] at 165°C, 12 MPa HZ, in the presence of a heterogeneous catalyst comprising 76% by weight of A1, calculated as A1203, 4% by weight of Cu, calculated as CuO, 10% by weight of Co, calculated as CoO, and 10% by weight of Ni, calculated as Ni0 (as described in DE-A-1 953 263), was rectified in a distillation apparatus comprising a 2.0 1 still pot with double-wall heating, a 70 cm mirrored glass column filled with 3 mm V2A wire helices (3.5 cm internal column diameter) and a column head with liquid splitter.
0050/48395 ca o23os2s2 2000-o3-2s As main fraction, 1.191 kg of slightly yellowish TAD having a purity of 99.9 (according to GC) were obtained at a pressure of 40-42 hPa and a temperature at the top of 99-102~C.
The TAD obtained became increasingly yellow during the following days, ie. it was not color-stable.
Storage time in days APHA color number Example 2:
In a 300 ml autoclave with stirrer and basket insert, about 70 g (0.45 mol) of yellowish TAD (purity according to GC:> 99.9%; APHA
color number: 72), which had been obtained as described in Example 1, was treated with hydrogen at a pressure of 10 MPa for 6 hours at 90~C in the presence of a heterogeneous catalyst comprising 76% by weight of A1, calculated as A1z03, 4% by weight of Cu, calculated as CuO, 10% by weight of Co, calculated as Co0 and 10% by weight of Ni, calculated as Ni0 (4 mm extrudates), which was present as a fixed bed in the basket insert.
The reaction product was then filtered. The purity of the colorless TAD obtained was 99.9% according to GC.
The APHA color number of the TAD was < 1 after a storage time of 50 days. Even after a storage time of 147 days, the TAD appeared colorless to the eye, ie. the APHA color number was < 10.
Example 3:
Carrying out the experiment as in Example 2 but using 5 g of Raney nickel as heterogeneous catalyst (suspended) gave, after filtration, colorless TAD having a purity of 99.9% according to GC and an APHA color number of 17 after a storage time of 50 days. After a storage time of 148 days, the APHA color number was 23.
In particular, the invention relates to a process for purifying 4-aminopiperidines of the formula I
I, R1 N~ R3 where R1 to R4 are C1-C6-alkyl, R1 and R2 and/or R3 and R4 together form a CHZ chain having from 2 to 5 carbon atoms, which have been prepared from the corresponding piperidin-4-ones of the formula II
II, R1 N~ R3 where the radicals R are as defined above, with subsequent distillation.
The 4-aminopiperidines which, owing to 2,2,6,6-substitution, eg.
tetraalkyl substitution, are designated as sterically hindered, are used in a variety of applications. In particular, they serve as intermediates in the preparation of UV stabilizers for synthetic polymers (see, for example: R. Gachter, H. Miiller (editors): Taschenbuch der Kunststoffadditive, Carl Hanser Verlag, Munich, 1979; F. Gugumus, Polym. Degrad. Stabil. 44 (1994), 299 - 322) and as chain regulators and stabilizers in the 30 preparation of polyamides (cf., for example: w0 952 84 43, DE-A-4 413 177).
0050/48395 CA o23os2s2 2000-o3-2s _ 2 It is of particular importance that the sterically hindered 4-aminopiperidines have not only a high chemical purity but also no or very little intrinsic color and that no discoloration takes place over a storage time of a number of months. This applies particularly when the 4-aminopiperidine is used for the preparation of stabilizers or employed directly as additive, since the product quality of these and thus also the quality of the stabilized polymers depends decisively on the chemical purity and, in particular, the color quality.
The sterically hindered 4-aminopiperidines are generally prepared industrially from dialkyl ketones, eg. acetone or acetone derivatives. The piperidines I can be obtained in a single step from the compounds by a catalytic ring-closure reaction in the presence of ammonia and hydrogen (DE-A-2 412 750) or from piperidin-4-ones II
O
II, R1 N~ R3 by aminative hydrogenation in one or two stages, for example catalytically. (See, for example DE-A-35 25 387, DE-A-2 040 975, DE-A-2 349 962, DE-A-26 21 870, EP-A-33 529, EP-A-42 119, Ep-A-303 279, EP-A-410 970, EP-A-611 137, EP-A-623 585 and DE-A-42 10 311).
The sterically hindered 4-aminopiperidines produced industrially are generally purified by distillation. (See, for example EP-A-33 529).
However, troublesome amounts of substances which give a color are still present, or are formed after a short time, in the 4-amino-2,2,6,6-tetraalkylpiperidines which are prepared using conventional processes.
0050/48395 Ca o23o52s2 2000-o3-2s According to DE-A-195 55 58, EP-A-28 555, US 3 819 710 and JP
01,160,947 CChem. Abstr. 111: 232081r), color-producing compounds in certain aminoalcohols, which compounds are formed in the preparation of the aminoalcohols from ethylene oxide and an appropriate amine, can be converted into less color-producing compounds by catalytic hydrogenation.
JP 06 25,410 CChem. Abstr. 12I: 56988n), JP-OS 48-52708 CChem.
Abstr. 80: 36697y), JP 05,345,821 CChem. Abstr. 120: 272327t), US
5 362 914 and EP-A-262 562 disclose that discolorations in certain polyamines can be reduced by treatment with hydrogen in the presence of hydrogenation catalysts.
DE-A-22 05 958 discloses a process for purifying tertiary amines which have been obtained by reacting primary alcohols with ammonia, by hydrogenation of the impurities before the final distillation of the tertiary amine.
The abovementioned compounds are different classes of substances from those of the sterically hindered 4-amino-piperidines of the present invention. Furthermore, the origin of the color producing impurities in the abovementioned compounds lies in the specific preparative processes and starting materials employed in each case.
Japanese Patent Application JP-OS 02-311 457 describes the purification of 2,2,6,6-tetraalkyl-4-piperidinones by treatment with hydrogen in the presence of a hydrogenation catalyst.
According to the examples given in this application, the process product (triacetoneamine, TAA) is so color-unstable that it has a much poorer color quality than the starting material after just one week's storage at 60°C.
The development of preparative methods for chemically pure sterically hindered 4-aminopiperidines having low discoloration has taken a completely different route:
DD-A-266 799 teaches reacting 4-amino-2,2,6,6-tetramethyl-piperidine in acetone/water solution with C02, separating off the precipitate, washing with acetone, subsequently decomposing thermally and purifying the product by distillation.
SU 18 11 527 describes a different purification process for sterically hindered 4-aminopiperidines I. In that process, the contaminated crude product is dissolved in an aprotic solvent, 0050/48395 CA o23os2s2 2000-o3-2s reacted with ethylene glycol, the reaction product is isolated, the 4-aminopiperidine is set free using aqueous alkali and is, after removal of the aqueous phase, fractionally distilled.
Both processes are extraordinarily complicated and costly.
Finally, the earlier German Application No. 19622269.9 describes a distillation process for purifying crude 4-amino-piperidines I
by' in a first step, removing high-boiling substances and possibly water from the crude piperidines by distillation, in a second step adding from 0.01 to 5~ by weight, based on the product of the first step, of a reducing agent, for example sodium borohydride, and, in a third step, isolating the plperidines I by distillation.
It is an object of the present invention to provide an inexpensive process which is simple to carry out and by means of which colorless, color-stable and highly pure sterically hindered 4-aminopiperidines, eg. of the formula I, can be made available.
This means products whose very low intrinsic coloration is maintained for a prolonged period and which have, at the same time, a low by-product content and contain no stabilizing auxiliaries. The reference to the 4-aminopiperidines I as "colorless" includes a minimum discoloration, namely up to a color number of at most 40 APHA (measured in accordance with DIN-ISO 6271).
We have found that this object is achieved by a process for purifying 2,2,6,6-tetrasubstituted 4-aminopiperidines which have been prepared from the corresponding piperidin-4-ones with subsequent distillation, which comprises reacting the distilled 2,2,6,6-tetrasubstituted 4-aminopiperidine with hydrogen in the presence of a hydrogenation or dehydrogenation catalyst and then again separating the 4-aminopiperidine from the reaction mixture.
In the sterically hindered 4-aminopiperidines I, the radicals R1, RZ, R3 and R4, independently of one another, are preferably C1-C3-alkyl, for example ethyl or methyl, in particular methyl.
The pure but discolored and/or color-unstable 4-amino-piperidine, eg. of the formula I, which has been obtained according to known methods by reaction of the corresponding piperidin-4-one, for example by aminative hydrogenation, and subsequent fractional rectification, is, according to the present invention, reacted with hydrogen in the presence of a hydrogenation catalyst, for example at from 20 to 200~C. Higher temperatures are also 0050/48395 ca o23os2s2 2000-o3-2s possible. Preference is given to a reaction temperature in the range from 50 to 150~C.
The reaction of the 4-aminopiperidine with hydrogen can be 5 carried out at atmospheric pressure or preferably under superatmospheric pressure, for example from 0.1 to 50 MPa. Higher pressures are also possible. Preference is given to a reaction pressure of from 1 to 30 MPa, in particular from 1 to 20 MPa.
The reaction of the 4-aminopiperidine with hydrogen can be carried out in the presence of a solvent or a solvent mixture which is inert under the reaction conditions, or preferably in the absence of solvent. When using a solvent, for example tetrahydrofuran, dioxane, 1,2-dimethoxyethane, methanol or ethanol, the reaction conditions are selected such that the solvent is present in liquid form in the reaction mixture.
As regards the hydrogenation catalysts which can be used, there are no restrictions. Dehydrogenation catalysts can also be used.
Suitable hydrogenation catalysts are, for example, catalysts which comprise copper, silver, gold, iron, cobalt, nickel, ruthenium, rhodium, palladium, rhenium, osmium, iridium, platinum, chromium, molybdenum or a mixture thereof.
The hydrogenation catalyst used can be homogeneously dissolved in the 4-aminopiperidine or in the mixture of 4-aminopiperidine and solvent, for example when using tris(triphenylphosphine)rhodium chloride, or, particularly preferably, be present in undissolved form, ie. heterogeneous.
Suitable heterogeneous catalysts are support-free catalysts such as Raney nickel or Raney cobalt, with the latter being present as a suspension in the reaction mixture, or supported catalysts which are preferably arranged as a fixed bed in the reactor. In the case of the supported catalysts, suitable support materials for the catalytically active metals or metal compounds are, for example, carbon, aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide, zinc oxide, magnesium oxide, silicon carbide, zeolites or mixtures thereof.
Examples which may be mentioned are supported catalysts comprising copper and/or cobalt and/or nickel and aluminum oxide and/or zirconium dioxide.
0050/48395 ca o23os2s2 2000-o3-2s For example, the two supported catalysts having the following compositions can be employed:
76% by weight of A1, calculated as A1203, 4% by weight of Cu, calculated as CuO, 10% by weight of Co, calculated as CoO, and 10% by weight of Ni, calculated as Ni0 (as described in DE-A-1 953 263) °r 31.5% by weight of Zr, calculated as Zr02, 50% by weight of Ni, calculated as NiO, 17% by weight of Cu, calculated as CuO, and 1.5% of Mo, calculated as Mo03 (as described in EP-A-696 572).
The necessary residence time of the 4-aminopiperidine over the catalyst is determined, inter alia, by the degree of discoloration of the distilled 4-aminopiperidine and by the desired decolorization and/or color stability of the piperidine.
As a rule, the residence time is longer, the higher the degree of discoloration of the 4-aminopiperidine used in the process step of the present invention and the higher the color quality requirements for the product.
Depending on the reaction conditions selected, residence times of from 10 minutes to a few hours are generally sufficient.
The process step of the present invention can be carried out either continuously, for example in tube reactors, stirred vessels or cascades of stirred vessels, or batchwise, for example in stirred vessels.
After carrying out the process step of the present invention, the 4-aminopiperidine is separated from the hydrogenation catalyst and from any solvent used.
Hydrogenation catalysts dissolved in the reaction product are separated off by distillation, with any solvent used and the 4-aminopiperidine being taken off in succession at the top in a customary manner.
Hydrogenation catalysts used in suspension are separated off by decantation and/or filtration. The reaction product can subsequently be distilled, which is in any case necessary if a solvent is used.
0050/48395 Ca o23o52s2 2000-o3-2s When using a hydrogenation catalyst arranged as a fixed bed, the reaction product is advantageously filtered in order to remove any abraded catalyst present. The reaction product can subsequently be distilled, which is in any case necessary if a solvent is used.
The process of the present invention gives, in a simple, inexpensive manner, pure sterically hindered 4-aminopiperidines which have virtually no intrinsic color and remain color-stable on storage, so that the addition of stabilizers is superfluous.
Examples The color of the sterically hindered 4-aminopiperidines was determined by measuring the APHA color number in accordance with DIN-ISO 6271.
In all examples, the storage of the TAD samples was carried out under comparable conditions (room temperature, in the dark).
Example 1 (Comparative Example):
1.632 kg of crude synthetic product having the composition (in %
by weight) 85.6% of 4-amino-2,2,6,6-tetramethylpiperidine (triacetonediamine, TAD) 9.0% of Hz0 about 0.7% of NH3 1.4% of 4-hydroxy-2,2,6,6-tetramethylpiperidine (triacetoneaminoalcohol,TAA-ol) 3.3% of by-products including high boilers, which had been obtained by aminative hydrogenation of 2,2,6,6-tetramethylpiperidin-4-one (triacetoneamine, TAA) [GC
purity: 99%; APHA color number: about 370 (measured as a 1%
strength solution in ethanol)] at 165°C, 12 MPa HZ, in the presence of a heterogeneous catalyst comprising 76% by weight of A1, calculated as A1203, 4% by weight of Cu, calculated as CuO, 10% by weight of Co, calculated as CoO, and 10% by weight of Ni, calculated as Ni0 (as described in DE-A-1 953 263), was rectified in a distillation apparatus comprising a 2.0 1 still pot with double-wall heating, a 70 cm mirrored glass column filled with 3 mm V2A wire helices (3.5 cm internal column diameter) and a column head with liquid splitter.
0050/48395 ca o23os2s2 2000-o3-2s As main fraction, 1.191 kg of slightly yellowish TAD having a purity of 99.9 (according to GC) were obtained at a pressure of 40-42 hPa and a temperature at the top of 99-102~C.
The TAD obtained became increasingly yellow during the following days, ie. it was not color-stable.
Storage time in days APHA color number Example 2:
In a 300 ml autoclave with stirrer and basket insert, about 70 g (0.45 mol) of yellowish TAD (purity according to GC:> 99.9%; APHA
color number: 72), which had been obtained as described in Example 1, was treated with hydrogen at a pressure of 10 MPa for 6 hours at 90~C in the presence of a heterogeneous catalyst comprising 76% by weight of A1, calculated as A1z03, 4% by weight of Cu, calculated as CuO, 10% by weight of Co, calculated as Co0 and 10% by weight of Ni, calculated as Ni0 (4 mm extrudates), which was present as a fixed bed in the basket insert.
The reaction product was then filtered. The purity of the colorless TAD obtained was 99.9% according to GC.
The APHA color number of the TAD was < 1 after a storage time of 50 days. Even after a storage time of 147 days, the TAD appeared colorless to the eye, ie. the APHA color number was < 10.
Example 3:
Carrying out the experiment as in Example 2 but using 5 g of Raney nickel as heterogeneous catalyst (suspended) gave, after filtration, colorless TAD having a purity of 99.9% according to GC and an APHA color number of 17 after a storage time of 50 days. After a storage time of 148 days, the APHA color number was 23.
Claims (9)
1. A process for purifying 2,2,6,6-tetrasubstituted 4-amino-piperidines which have been prepared from the corresponding piperidin-4-ones with subsequent distillation, which comprises reacting the distilled 2,2,6,6-tetrasubstituted 4-aminopiperidine with hydrogen in the presence of a hydrogenation or dehydrogenation catalyst and separating the 4-aminopiperidine from the reaction mixture.
2. A process as claimed in claim 1 for purifying 4-amino-piperidines of the formula I
where R1 to R4 are C1-C6-alkyl, R1 and R2 and/or R3 and R4 together form a CH2 chain having from 2 to 5 carbon atoms, which have been prepared from the corresponding piperidin-4-ones of the formula II
where R1 to R4 are as defined above.
where R1 to R4 are C1-C6-alkyl, R1 and R2 and/or R3 and R4 together form a CH2 chain having from 2 to 5 carbon atoms, which have been prepared from the corresponding piperidin-4-ones of the formula II
where R1 to R4 are as defined above.
3. A process as claimed in claim 1 for purifying 4-amino-piperidines of the formula I as defined in claim 2 in which R1, R2, R3 and R4 are methyl.
4. A process as claimed in any of claims 1 to 3, wherein the reaction with hydrogen is carried out at from 20 to 200°C.
5. A process as claimed in any of claims 1 to 4, wherein the reaction is carried out at pressures of from 1 to 30 MPa.
6. A process as claimed in any of claims 1 to 5, wherein the reaction is carried out in the absence of a solvent.
7. A process as claimed in any of claims 1 to 6, wherein the hydrogenation catalyst comprises copper, silver, gold, iron, cobalt, nickel, ruthenium, rhodium, palladium, rhenium, osmium, iridium, platinum, chromium, molybdenum or a mixture thereof.
8. A process as claimed in any of claims 1 to 7, wherein the hydrogenation catalyst used is a supported catalyst.
9. A process as claimed in any of claims 1 to 8, wherein the hydrogenation catalyst used is a supported catalyst comprising nickel and/or copper and/or cobalt and aluminum oxide and/or zirconium dioxide.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19743433.9 | 1997-10-01 | ||
DE19743433A DE19743433C1 (en) | 1997-10-01 | 1997-10-01 | Process for the purification of 4-amino-piperidines |
PCT/EP1998/006117 WO1999016749A1 (en) | 1997-10-01 | 1998-09-25 | Method for purifying 4-amino-piperidines |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2305282A1 true CA2305282A1 (en) | 1999-04-08 |
Family
ID=7844311
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002305282A Abandoned CA2305282A1 (en) | 1997-10-01 | 1998-09-25 | Method for purifying 4-amino-piperidines |
Country Status (16)
Country | Link |
---|---|
EP (1) | EP1025084A1 (en) |
JP (1) | JP2001518465A (en) |
KR (1) | KR20010030840A (en) |
CN (1) | CN1272843A (en) |
AU (1) | AU9746998A (en) |
BR (1) | BR9812595A (en) |
CA (1) | CA2305282A1 (en) |
CO (1) | CO4770994A1 (en) |
DE (1) | DE19743433C1 (en) |
HU (1) | HUP0004584A2 (en) |
ID (1) | ID23897A (en) |
NZ (1) | NZ503565A (en) |
PL (1) | PL339578A1 (en) |
SK (1) | SK4262000A3 (en) |
TW (1) | TW377345B (en) |
WO (1) | WO1999016749A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2085384A1 (en) | 2008-02-01 | 2009-08-05 | Evonik Degussa GmbH | Method of manufacturing 4-Amino-2,2,6,6-tetramethylpiperidin |
DE102008040045A1 (en) * | 2008-02-01 | 2009-08-06 | Evonik Degussa Gmbh | Process for the preparation of 4-amino-2,2,6,6-tetramethylpiperidine |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3003843A1 (en) * | 1980-02-02 | 1981-08-13 | Chemische Werke Hüls AG, 4370 Marl | METHOD FOR PRODUCING 4-AMINO-2,2,6,6-TETRAMETHYL PIPERIDINE |
CH664361A5 (en) * | 1985-06-13 | 1988-02-29 | Ni Institutkhimikatov Dlya Pol | METHOD FOR PRODUCING 4-Amino-2,2,6,6-tetramethylpiperidine. |
US4766247A (en) * | 1986-09-26 | 1988-08-23 | Air Products And Chemicals, Inc. | Color reduction of polyamines by mild catalytic hydrogenation |
JP2718179B2 (en) * | 1989-05-26 | 1998-02-25 | 三井化学株式会社 | Method for purifying 2,2,6,6-tetraalkyl-4-piperidinone |
DE19622269A1 (en) * | 1996-06-03 | 1997-12-04 | Basf Ag | Process for the purification of sterically hindered 4-aminopiperidines |
-
1997
- 1997-10-01 DE DE19743433A patent/DE19743433C1/en not_active Expired - Lifetime
-
1998
- 1998-09-25 NZ NZ503565A patent/NZ503565A/en unknown
- 1998-09-25 BR BR9812595-8A patent/BR9812595A/en not_active Application Discontinuation
- 1998-09-25 ID IDW20000612D patent/ID23897A/en unknown
- 1998-09-25 CN CN98809761A patent/CN1272843A/en active Pending
- 1998-09-25 EP EP98951469A patent/EP1025084A1/en not_active Withdrawn
- 1998-09-25 SK SK426-2000A patent/SK4262000A3/en unknown
- 1998-09-25 JP JP2000513835A patent/JP2001518465A/en not_active Withdrawn
- 1998-09-25 AU AU97469/98A patent/AU9746998A/en not_active Abandoned
- 1998-09-25 HU HU0004584A patent/HUP0004584A2/en unknown
- 1998-09-25 PL PL98339578A patent/PL339578A1/en unknown
- 1998-09-25 CA CA002305282A patent/CA2305282A1/en not_active Abandoned
- 1998-09-25 KR KR1020007003498A patent/KR20010030840A/en not_active Application Discontinuation
- 1998-09-25 WO PCT/EP1998/006117 patent/WO1999016749A1/en not_active Application Discontinuation
- 1998-09-30 CO CO98056932A patent/CO4770994A1/en unknown
- 1998-09-30 TW TW087116216A patent/TW377345B/en active
Also Published As
Publication number | Publication date |
---|---|
ID23897A (en) | 2000-05-25 |
JP2001518465A (en) | 2001-10-16 |
DE19743433C1 (en) | 1999-04-22 |
WO1999016749A1 (en) | 1999-04-08 |
CO4770994A1 (en) | 1999-04-30 |
SK4262000A3 (en) | 2000-10-09 |
TW377345B (en) | 1999-12-21 |
PL339578A1 (en) | 2000-12-18 |
EP1025084A1 (en) | 2000-08-09 |
BR9812595A (en) | 2000-08-01 |
KR20010030840A (en) | 2001-04-16 |
HUP0004584A2 (en) | 2001-04-28 |
AU9746998A (en) | 1999-04-23 |
CN1272843A (en) | 2000-11-08 |
NZ503565A (en) | 2001-09-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR100392945B1 (en) | Method for producing ε-caprolactam and ε-caprolactam precursors | |
AU2006300492B2 (en) | Process for producing 1-benzyl-4-[(5,6-dimethoxy-1indanon)-2-yl]methylpiperidine or hydrochloride thereof | |
JPH10218860A (en) | Production of n-monosubstituted 4-aminopiperidine | |
EP0611137B1 (en) | Process for producing amines starting from cyclic ketones | |
KR101658666B1 (en) | Process for the preparation of 4-amino-2,2,6,6-tetramethylpiperidine | |
CA2305282A1 (en) | Method for purifying 4-amino-piperidines | |
US4923992A (en) | Process for the preparation of bis(2,2,6,6-tetramethyl-4-piperidyl)amine | |
KR20230154915A (en) | Method for producing N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine | |
MXPA00002989A (en) | Method for purifying 4-amino-piperidines | |
CZ20001042A3 (en) | Purification process of 4-amino-piperidines | |
CA2257095C (en) | Process for purifying sterically hindered 4-amino piperidines | |
CA2257094C (en) | Sterically hindered 4-amino-piperidine with a low dimer content, its production and use | |
JP7140347B2 (en) | Method for producing 4-(piperidin-4-yl)morpholine | |
KR100502425B1 (en) | Method for preparing 4-amino-1-butanol | |
JPH07116146B2 (en) | Process for producing 4-piperidinopiperidines | |
KR100458246B1 (en) | Three-dimensionally shielded 4-amino-piperidine with a low dimer content, preparation method and use thereof | |
JPS63192751A (en) | Production of 4-hydroxypiperidine | |
WO2000012476A9 (en) | Processes for preparing 2-piperidineethanol compounds | |
KR20000016253A (en) | Process for purifying sterically hindered 4-amino piperidines |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FZDE | Discontinued |