CN1272843A - 4-氨基哌啶的纯化方法 - Google Patents
4-氨基哌啶的纯化方法 Download PDFInfo
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- BCIIMDOZSUCSEN-UHFFFAOYSA-N piperidin-4-amine Chemical class NC1CCNCC1 BCIIMDOZSUCSEN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004821 distillation Methods 0.000 claims abstract description 8
- 239000011541 reaction mixture Substances 0.000 claims abstract description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 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
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 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
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 238000006356 dehydrogenation reaction Methods 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
- 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
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 230000000694 effects Effects 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
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- VRJHQPZVIGNGMX-UHFFFAOYSA-N 4-piperidinone Chemical class O=C1CCNCC1 VRJHQPZVIGNGMX-UHFFFAOYSA-N 0.000 abstract description 2
- -1 2,2,6,6-tetrasubstituted 4-amino-piperidines Chemical class 0.000 abstract 2
- 230000000887 hydrating effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 241001550224 Apha Species 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005562 fading Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000003053 piperidines Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005576 amination reaction Methods 0.000 description 3
- 150000001414 amino alcohols Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- FTVFPPFZRRKJIH-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-amine Chemical class CC1(C)CC(N)CC(C)(C)N1 FTVFPPFZRRKJIH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- JWUXJYZVKZKLTJ-UHFFFAOYSA-N Triacetonamine Chemical compound CC1(C)CC(=O)CC(C)(C)N1 JWUXJYZVKZKLTJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-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
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- BDDWSAASCFBVBK-UHFFFAOYSA-N rhodium;triphenylphosphane Chemical compound [Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 BDDWSAASCFBVBK-UHFFFAOYSA-N 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000000926 separation method 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
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000003313 weakening effect Effects 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
一种纯化2,2,6,6-四取代的4-氨基—哌啶的方法,该2,2,6,6-四取代的4-氨基—哌啶由相应的哌啶-4-酮制备随后蒸馏,该方法包括在氢化或去氢作用催化剂存在的条件下将蒸馏的2,2,6,6-四取代的4-氨基哌啶与氢反应并从反应混合物中分离出4-氨基哌啶。
Description
本发明涉及一种纯化2,2,6,6-四取代的4-氨基哌啶的方法,该2,2,6,6-四取代的4-氨基哌啶是由相应的哌啶-4-酮制备随后蒸馏而得。
本发明特别涉及一种纯化式I的4-氨基哌啶的方法。
其中基团R如上所述。
4-氨基哌啶由于2,2,6,6-取代如四烷基取代,被称为是空间位阻的,在很多方面有应用。特别地,它们在制备用于合成聚合物的UV稳定剂中用作中间体(参见,例如:R.Gchter,H.Müller(编者):Taschenbuch der Kunststoffadditive,Carl Hanser Verlag,Munich,1979;F.Gugumus,Polym.Degrad.Stabil.44(1994),299-322)和在制备聚酰胺时充当链调节剂和稳定剂(参阅,例如:WO 952 84 43,DE-A-4 413177)。
非常重要的是空间位阻的4-氨基哌啶不仅具有很高的化学纯度而且没有或几乎没有本体颜色,所以经过数月的存贮并不发生褪色现象。这一点特别应用于4-氨基哌啶用于制备稳定剂或直接用作添加剂,因为这些产品的质量并因而稳定的聚合物的质量决定性地取决于化学纯度并且特别是颜色质量。
在一或两阶段内通过胺化氢化作用,例如催化而得到(参见,例如: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和DE-A-42 10311)。
工业上生产的空间位阻的4-氨基哌啶通常通过蒸馏进行纯化。(参见如:EP-A-33 529)。
然而,在用常规方法制备的4-氨基-2,2,6,6-四烷基哌啶中讨厌的一定量的产生颜色的物质仍然存在,或短时间后即形成。
根据DE-A-195 55 58、EP-A-28 555、US 3 819 710和JP 01,160,947(化学文摘111:232081r),某些氨基醇中产生颜色的化合物,该化合物在由环氧乙烷和适当的胺来制备氨基醇时形成,可以通过催化氢化转化成产生颜色较少的化合物。
JP 06 25,410(化学文摘121:56988n)、JP-OS 48-52708(化学文摘80:36697y)、JP 05,345,821(化学文摘120:272327t)、US 5 362914和EP-A-262 562都公开了某些聚胺中的褪色现象可通过在氢化作用催化剂存在的条件下用氢处理而减弱。
DE-A-22 05 958公开了一种通过在叔胺最后蒸馏之前将杂质氢化而纯化叔胺的方法,该叔胺是通过伯醇与氨反应而得。
上述化合物是与本发明的空间位阻的4-氨基-哌啶 不同类别的物质。另外,上述化合物中产生颜色的杂质的来源在于每种情况下具体的制备方法和所用的起始物质。
日本专利申请JP-OS 02-311 457描述了通过在氢化作用催化剂存在的条件下用氢处理来纯化2,2,6,6-四烷基-4-哌啶酮。根据此申请中所给的实施例,该方法的产物(三丙酮胺,TAA)是颜色非常不稳定的以至于在60℃仅仅贮存一周后它就比起始材料的颜色质量差很多。
具有低的褪色作用的化学纯空间位阻4-氨基哌啶的制备方法的研究采用了完全不同的路线:
DD-A-266 799指出将4-氨基-2,2,6,6-四甲基-哌啶在丙酮/水溶液中与CO2反应,分离出沉淀,用丙酮冲洗,接着热分解并通过蒸馏纯化产物。
SU 18 11 527描述了空间位阻的4-氨基哌啶I的纯化方法。在该方法中,污染的粗产物溶解于非质子传递的溶剂中,与乙二醇反应,分离反应产物,用碱水释放出4-氨基哌啶,并在除去水相后,进行分馏。
这两种方法都格外复杂和费用高。
最后,早先的德国申请No.196 222 69.9描述了一种纯化粗4-氨基-哌啶I的蒸馏方法,第一步中,通过蒸馏从粗的哌啶中除去高沸点物质和可能的水,第二步中加入0.01-5%重量的还原剂,例如硼氢化钠,以第一步的产物为基准,在第三步中,通过蒸馏分离出哌啶I。
本发明的目的在于提供一种便宜的方法,它实施简单且通过此方法可制得无色、颜色稳定和高纯度的空间位阻的4-氨基哌啶,如式I的4-氨基哌啶。这意味着产物经过很长一段时期仍保持很低的本体显色现象并且同时具有很低的副产物含量且不含稳定助剂。称4-氨基哌啶I为“无色”包括最低限度的褪色,即最高色数至多40APHA(根据DIN-ISO6271测定)。
我们发现此目的由一种纯化2,2,6,6-四取代4-氨基哌啶的方法实现了,该2,2,6,6-四取代4-氨基哌啶是由相应的哌啶-4-酮制备随后进行蒸馏而得,该方法包括将蒸馏的2,2,6,6-四取代4-氨基哌啶与氢在一种氢化或去氢作用催化剂存在下反应,然后再从反应混合物中分离4-氨基哌啶。在空间位阻的4-氨基哌啶I中,基团R1、R2、R3和R4各自独立,优选为C1-C3烷基,例如乙基或甲基,特别是甲基。
根据本发明,纯净但褪色和/或颜色不稳定的4-氨基-哌啶,如式I的4-氨基-哌啶,它是根据已知方法通过相应的哌啶-4-酮的反应如胺化氢化作用并随后分级精馏而得,在氢化催化剂存在的条件下例如在20-200℃与氢反应。高温也是可以的。优选的反应温度范围是50-150℃。
4-氨基哌啶与氢的反应可在常压下完成或优选超计大气压,例如0.1-50MPa。更高压也是可以的。优选反应压力为1-30MPa,特别是1-20MPa。
4-氨基哌啶与氢的反应可在反应条件下为惰性的一种溶剂或一种溶剂混合物存在的条件下完成,或优选没有溶剂存在。使用溶剂时,例如四氢呋喃、二噁烷、1,2-二甲氧基乙烷、甲醇或乙醇,要选择反应条件以便溶剂在反应混合物中以液体形式存在。
关于可用的氢化催化剂,没有什么限制。去氢催化剂也可使用。
适合的氢化催化剂例如包括铜、银、金、铁、钴、镍、钌、铑、钯、铼、锇、铱、铂、铬、钼或它们的混合物。
所用的氢化催化剂可以均匀地溶解于4-氨基哌啶中或溶于4-氨基哌啶和溶剂的混合物中,例如在使用三(三苯膦)铑氯化物时,或者特别优选以不溶的形式,即不均匀的形式存在。
适合的不均匀催化剂为没有载体的催化剂如阮内镍或阮内钴催化剂,后者作为反应混合物中的悬浮体存在,或者为载体催化剂,优选将其安排成反应器中的固定床。在载体催化剂的情况下,对于催化活性的金属或金属化合物来说适合的载体材料为,例如:碳、氧化铝、二氧化硅、二氧化钛、二氧化锆、氧化锌、氧化镁、碳化硅、沸石或它们的混合物。
可提及的载体催化剂的例子包括铜和/或钴和/或镍和氧化铝和/或二氧化锆。
例如,可以使用具有如下组成的两种载体催化剂:
76%重量的Al,以Al2O3计算,4%重量的Cu,以CuO计算,10%重量的Co,以CoO计算,和10%重量的Ni,以NiO计算(如DE-A-1953263中所述),
或者31.5%重量的Zr,以ZrO2计算,50%重量的镍,以NiO计算,17%重量的Cu,以CuO计算,和1.5%重量的Mo,以MoO3计算(如EP-A-696 572中所述)。
特别通过蒸馏的4-氨基哌啶的褪色程度和通过所需的哌啶的褪色作用和/或颜色稳定性来决定4-氨基哌啶在催化剂上所需的滞留时间。一般来说,滞留时间越长,本发明的方法步骤中所用的4-氨基哌啶的褪色程度越高并且对产品的颜色质量要求越高。
根据反应条件,10分钟到几小时的滞留时间通常就足够了。
本发明的方法步骤既可以连续进行,例如在管式反应器、搅拌容器或级联搅拌容器中,也可以分批进行,例如在搅拌容器中。
在完成了本发明的工步骤之后,将4-氨基哌啶从氢化催化剂和可能使用的任何溶剂中分离出来。
溶于反应产物的氢化催化剂通过蒸馏分离出来,所用的任何溶剂和4-氨基哌啶在常规方法中在顶部连续蒸馏移走。
悬浮液中所用的氢化催化剂通过倾析和/或过滤分离出去。可将反应产物随后蒸馏,如果使用溶剂这在任何情况下都是需要的。
当使用安排为固定床的氢化催化剂时,比较有利的是将反应产物过滤以除去任何存在的磨耗的催化剂。随后可将反应产物蒸馏,如果使用溶剂这在任何情况下都是需要的。
本发明的方法用简单、廉价的方式提供了纯净的空间位阻4-氨基哌啶,它实质上不具有本体颜色并且贮存时保持颜色稳定,所以添加稳定剂是多余的。
实施例:
根据DIN-ISO 6271通过测定APHA色数来测定空间位阻的4-氨基哌啶的颜色。
在所有的实施例中,TAD样品的存贮在可比较条件下进行(室温,黑暗中)。
实施例1(比较实施例):
1.632kg粗的合成产物,具有如下组成(以%重量计):
85.6%的4-氨基-2,2,6,6-四甲基哌啶(三丙酮二胺,TAD)
9.0%的H2O
大约0.7%的NH3
1.4%的4-羟基-2,2,6,6-四甲基哌啶(三丙酮氨基醇,TAA-醇)
3.3%的副产物,包括高沸点的,
该合成产物是通过2,2,6,6-四甲基哌啶-4-酮(三丙酮胺,TAA)[GC纯度:99%;APHA色数:大约370(由1%浓度的在乙醇中的溶液测定)]在165℃,12MPa H2下,在不均匀催化剂存在的条件下胺化氢化而得到的,该不均匀催化剂包括76%重量的Al,以Al2O3计算,4%重量的Cu,以CuO计算,10%重量的Co,以CoO计算,和10%重量的Ni,以NiO计算(如DE-A-1 953 263中所述),将该粗的合成产物在蒸馏装置上精馏,该蒸馏装置包括一个2.0l带双层加热壁的蒸馏釜,一个70cm的用3mm V2A金属螺旋线填充的反射玻璃柱(3.5cm的柱内径)和一个带液体分流板的柱头。
作为主要馏分,1.191kg的淡黄色的纯度为99.9%(根据GC)的TAD在40-42 hPa压力下和顶部温度为99-102℃下得到。
所得的TAD在如下天数期间显著变黄,即它不是颜色稳定的。
存贮时间,以天计 APHA色数
5 145
70 268
实施例2:
在一个300 ml带搅拌器和篮形接头的高压釜中,大约70g(0.45mol)黄色的TAD(根据GC纯度≥99.9%;APHA色数:72),它是按实施例1所述而得,在不均匀催化剂存在的条件下在90℃在10MPa压力下用氢处理6小时,该催化剂包括76%重量的Al,以Al2O3计算,4%重量的铜,以CuO计算,10%重量的Co,以CoO计算和10%重量的Ni,以NiO(4mm挤出物)计算,它作为篮形接头中的固定床存在。
然后过滤反应产物。根据GC所得无色TAD的纯度为99.9%。贮存50天后TAD的APHA色数≤1。即使贮存147天后,TAD目视仍显无色,即:APHA色数<10。
实施例3:
按照实施例2进行实验,但用5g阮内镍作为不均匀催化剂(悬浮的),过滤后得到GC纯度99.9%的无色TAD,贮存50天后APHA色数为17。贮存148天后,APHA色数为23。
Claims (9)
1.一种纯化2,2,6,6-四取代的4-氨基-哌啶的方法,该2,2,6,6-四取代的4-氨基-哌啶由相应的哌啶-4-酮制备随后蒸馏,该方法包括在氢化或去氢作用催化剂存在的条件下将蒸馏的2,2,6,6-四取代的4-氨基哌啶与氢反应并从反应混合物中分离出4-氨基哌啶。
2.一种如权利要求1所述的纯化式I的4-氨基-哌啶的方法,
其中R1-R4为C1-C6烷基,R1和R2和/或R3和R4共同形成一个具有2-5个碳原子的CH2链,该4-氨基-哌啶是由式II相应的哌啶-4-酮制备,
其中R1-R4如上所述。
3.一种如权利要求1所述的纯化如权利要求2所定义的式I的4-氨基-哌啶的方法,其中R1、R2、R3和R4为甲基。
4.一种如权利要求1-3中任一项所述的方法,其中与氢的反应在20-200℃下完成。
5.一种如权利要求1-4中任一项所述的方法,其中反应在1-30MPa的压力下完成。
6.一种如权利要求1-5中任一项所述的方法,其中反应在没有溶剂存在的条件下完成。
7.一种如权利要求1-6中任一项所述的方法,其中氢化催化剂包括铜、银、金、铁、钴、镍、钌、铑、钯、铼、锇、铱、铂、铬、钼或它们的混合物。
8.一种如权利要求1-7中任一项所述的方法,其中所用的氢化催化剂为载体催化剂。
9.一种如权利要求1-8中任一项所述的方法,所用氢化催化剂是包括镍和/或铜和/或钴和氧化铝和/或二氧化锆的载体催化剂。
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DE19743433A DE19743433C1 (de) | 1997-10-01 | 1997-10-01 | Verfahren zur Reinigung von 4-Amino-piperidinen |
DE19743433.9 | 1997-10-01 |
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CO (1) | CO4770994A1 (zh) |
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PL (1) | PL339578A1 (zh) |
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EP2085384A1 (de) | 2008-02-01 | 2009-08-05 | Evonik Degussa GmbH | Verfahren zur Herstellung von 4-Amino-2,2,6,6-tetramethylpiperidin |
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DE3003843A1 (de) * | 1980-02-02 | 1981-08-13 | Chemische Werke Hüls AG, 4370 Marl | Verfahren zur herstellung von 4-amino-2,2,6,6-tetramethylpiperidin |
CH664361A5 (de) * | 1985-06-13 | 1988-02-29 | Ni Institutkhimikatov Dlya Pol | Verfahren zur herstellung von 4-amino-2,2,6,6-tetramethylpiperidin. |
US4766247A (en) * | 1986-09-26 | 1988-08-23 | Air Products And Chemicals, Inc. | Color reduction of polyamines by mild catalytic hydrogenation |
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DE19622269A1 (de) * | 1996-06-03 | 1997-12-04 | Basf Ag | Verfahren zur Reinigung von sterisch gehinderten 4-Aminopiperidinen |
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ID23897A (id) | 2000-05-25 |
JP2001518465A (ja) | 2001-10-16 |
HUP0004584A2 (hu) | 2001-04-28 |
SK4262000A3 (en) | 2000-10-09 |
TW377345B (en) | 1999-12-21 |
CA2305282A1 (en) | 1999-04-08 |
KR20010030840A (ko) | 2001-04-16 |
NZ503565A (en) | 2001-09-28 |
PL339578A1 (en) | 2000-12-18 |
WO1999016749A1 (de) | 1999-04-08 |
DE19743433C1 (de) | 1999-04-22 |
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