CN101541787B - N-烯丙基空间位阻的叔胺的制备方法 - Google Patents
N-烯丙基空间位阻的叔胺的制备方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 30
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- 150000001412 amines Chemical class 0.000 title abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- -1 hydrogen Chemical class 0.000 claims description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 8
- 150000001721 carbon Chemical group 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 150000003335 secondary amines Chemical class 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 235000011089 carbon dioxide Nutrition 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
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- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
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- 239000004611 light stabiliser Substances 0.000 description 2
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- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
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- 125000000217 alkyl group Chemical group 0.000 description 1
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- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000003053 piperidines Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Hydrogenated Pyridines (AREA)
- Plural Heterocyclic Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明公开了制备式I化合物的方法：其中通用符号如权利要求1所定义，该方法包括：式II的空间位阻的胺其中通用符号如权利要求1所定义，与式III的化合物
Description
本发明涉及制备N-烯丙基空间位阻的叔胺的改进方法，该胺适合于使有机材料稳定，以防止氧化、热或光诱导的降解。
N-烯丙基取代的空间位阻的胺光稳定剂是如下制备的：在碱的存在下，在高温下，由相应的空间位阻的仲胺与烯丙基卤进行烷基化。
烯丙基卤的成本不断地提高，并且对这些N-烯丙基稳定剂的生产成本具有很大影响。使用烯丙基卤的进一步的缺点是这种合成路线形成盐副产物的事实，这种副产物对于环境是危险的，并且必须被除去。
因此，高度合乎需要的是，由相应空间位阻的仲胺制备N-烯丙基空间位阻叔胺的不含卤化物的方法。
现在已经发现，在催化剂的存在下，用二氧化碳作为活化剂，可以使空间位阻的胺与丙烯醇反应，形成所需要的N-烯丙基空间位阻的胺。
本发明因此涉及制备式I化合物的改进方法：
其中连接基团R与它直接连接的碳原子，以及氮原子，一起形成取代的5-、6-或7-元环状结构，
R1、R2、R3和R4彼此独立地是C1-C8烷基或C1-C5羟烷基，或R1和R2与它们相连接的碳原子一起是C5-C12环烷基，或R3和R4与它们相连接的碳原子一起是C5-C12环烷基，
R5、R6、R7、R8和R9彼此独立地是氢、C1-C8烷基、C2-C8烯基、未取代的或被C1-C4烷基、C1-C4烷氧基或卤素取代的C5-C12芳基；C1-C4卤代烷基、氰基、硝基、卤素或-COOR10；R7和R8一起还可以形成化学键，
R10是C1-C12烷基、C5-C12环烷基、C7-C9苯基烷基或苯基，
该方法包括：式II的化合物
其中R、R1、R2、R3和R4如上所述，与式III的化合物
其中R5、R6、R7、R8和R9如上所述，在催化剂的存在下进行反应。
具有至多12个碳原子的烷基是支链或直链的原子团，例如甲基，乙基，丙基，异丙基，正丁基，仲丁基，异丁基，叔丁基，2-乙基丁基，正戊基，异戊基，1-甲基戊基，1，3-二甲基丁基，正己基，1-甲基己基，正庚基，异庚基，1，1，3，3-四甲基丁基，1-甲基庚基，3-甲基庚基，正辛基，2-乙基己基，1，1，3-三甲基己基，1，1，3，3-四甲基戊基，壬基，癸基，十一烷基，1-甲基十一烷基，十二烷基或1，1，3，3，5，5-六甲基己基。
具有至多5个碳原子的羟烷基是支链或直链的原子团，优选其含有1至3个、尤其是1或2个羟基，例如，1-羟甲基，1-羟乙基，1-羟基丙基，1-羟基丁基，1-羟基丁基，2-羟乙基，2-羟基丙基，2-羟基丁基，2-羟基丁基，2-羟基丙基或3-羟基丁基。
C5-C12环烷基例如是环戊基，环己基，环庚基，环辛基，环壬基，环癸基，环十一烷基或环十二烷基。
具有2至8个碳原子的烯基是支链或直链的原子团，例如，乙烯基，丙烯基，2-丁烯基，3-丁烯基，异丁烯基，正2，4-戊二烯基，3-甲基-2-丁烯基或正2-辛烯基。
芳基代表遵从Debye-Hueckel规则的基团；优选C5-C12芳基是苯基和萘基。
卤素是例如氟、氯、溴或碘。
C7-C9苯基烷基例如是苄基，α-甲基苄基，α，α-二甲苄基或2-苯乙基。 优选苄基和α，α-二甲苄基。
具有至多4个碳原子的烷氧基是支链或直链的原子团，例如甲氧基，乙氧基，丙氧基，异丙氧基，正丁氧基或异丁氧基。
所考虑的是制备式I化合物的方法，其中R1、R2、R3和R4是甲基。
还考虑的是制备式I化合物的方法，其中R5、R6、R7、R8和R9是氢。
特别感兴趣的是制备式I化合物的方法，其中R是 ，和
R11是与三嗪环相连接的氮。
优选的是制备式I化合物的方法，其中
R是
R1、R2、R3和R4是甲基，
R5、R6、R7、R8和R9是氢，和
R11是与三嗪环相连接的氮。
还优选的是制备式I化合物的方法，其中式I的化合物是单体、低聚或聚合的空间位阻的胺光稳定剂的一部分。
优选，相对于每单位的式II的空间位阻的仲胺，以等摩尔至100倍过量来使用式III化合物，例如1至50倍过量，优选1至20倍过量，典型地1至4倍过量。
优选，催化剂是金属催化剂。使人感兴趣的是选自钯、铑、钌、锇、铜、镍、锰、铁和钴催化剂的金属催化剂。
优选，在制备式I化合物的方法中，相对于每单位的式II的空间位阻的仲胺，以0.01至30mol％的数量使用催化剂，优选0.01至20mol％，典型地0.1至10mol％。
还使人感兴趣的是制备式I化合物的方法，其中催化剂是含有膦配体的金属催化剂。
膦的实例是式IV的化合物
P(Q)3 (IV)
其中Q可以相同或不同，并且是例如具有1至10个碳的烷基、具有4至10个碳的环烷基和/或具有6至10个碳的芳基，其例子是甲基、丁基、 环己基、苯基、甲苯基。优选，至少一个是芳基，和最优选，配体是三芳基。
具有上述结构的合适配体的例子是下列：三甲基膦，三环己基膦，三(间磺基(sulfonato)苯基)膦(TPPTS)，三苯基膦，2，2′-二(二苯基膦基)-1，1′-联二萘(BINAP)。优选的配体是三苯基膦。
优选，配体的数量是每个金属原子1至10摩尔。尤其优选的配体/原子金属比是2至6。
特别感兴趣的是制备式I化合物的方法，其中催化剂是(四三苯基膦)钯。
制备式I化合物的方法可以另外包括溶剂和/或碱。
本发明方法的有用溶剂是例如饱和和芳香烃、酮、酯、水或醇或其混合物。优选，溶剂可以是式III的化合物(烯丙醇)。尤其优选的有机溶剂的例子是甲苯、二甲苯、丙酮、甲醇或乙酸乙酯。
在性质上，碱是无机或有机碱。特别感兴趣的碱是例如碳酸钠、碳酸钾、氢氧化钠、三乙胺或吡啶。
在制备式I化合物的本发明方法中，反应温度是例如10和180℃之间，优选在20和140℃之间，和1至30个绝对大气压，优选1至15个绝对大气压的压力下。
还特别感兴趣的是制备式I化合物的方法，其中还存在二氧化碳或另一种惰性气体或其混合物。惰性气体的例子是例如氮气或氩气。优选，使用包括二氧化碳和氮气的惰性气体混合物。
下列实施例进一步举例说明本发明。份数或百分数是指重量。
实施例1：由化合物A起始，制备化合物101。
在配备机械搅拌器、冷凝器和含有CO2的橡皮气囊的圆底烧瓶中，将7.0g(Mw 3889，23.27mmol哌啶单元)化合物A[按照U.S.6,117,995的实施例1制备]、2.7g(46.9mmol)烯丙醇、0.46g(0.4mmol)(四三苯基膦)钯和2.37g(22.8mmol)三乙胺加入到25mL甲苯中。将混合物在50℃搅拌22小时。然后，用1H-NMR分析粗品反应物，显示：化合物A的2，2，6，6-四甲基哌啶单元的47％N-H基团转变为相应的N-烯丙基，由此形成化合物101。
实施例2：化合物102的制备。
在配备机械搅拌器的高压釜中，将7.12g(10.0mmol)2，4，6-三(N-正丁基-N-2，2，6，6-四甲基哌啶-4-基))-1，3，5-三嗪、3.45g(60mmol)烯丙醇、0.57g(0.5mmol)(四三苯基膦)钯加入到30mL丙酮中。然后，用CO2将氛围饱和，并将反应混合物在强烈搅拌下、在30℃保持60小时。然后，用 1H-NMR分析粗品反应物，显示：2，4，6-三(N-正丁基-N-2，2，6，6-四甲基哌 啶-4-基)-1，3，5-三嗪的2，2，6，6-四甲基哌啶单元的70％N-H基团转变为相应的N-烯丙基，由此形成化合物102。
实施例3：化合物102(参见实施例2中的化学式)的制备。
在配备机械搅拌器的高压釜中，将5.00g(7.0mmol)2，4，6-三(N-正丁基-N-2，2，6，6-四甲基哌啶-4-基))-1，3，5-三嗪、4.89g(84.2mmol)烯丙醇加入到25mL甲苯中。然后，将0.16g(0.7mmol)乙酸钯和0.37g(1.4mmol)三苯基膦连续地加入到该溶液(保持在氮气氛中)中。在强烈搅拌下，在80℃，使反应混合物反应16小时。然后，用1H-NMR分析粗品反应物，显示：2，4，6-三(N-正丁基-N-2，2，6，6-四甲基哌啶-4-基)-1，3，5-三嗪的2，2，6，6-四甲基哌啶单元的19％N-H基团转变为相应的N-烯丙基，由此形成化合物102。
Claims (10)
1.制备式I化合物的方法，
其中连接基团R与它直接连接的碳原子，以及氮原子，一起形成取代的5-、6-或7-元环状结构，
R1、R2、R3和R4彼此独立地是C1-C8烷基或C1-C5羟烷基，或R1和R2与它们相连接的碳原子一起是C5-C12环烷基，或R3和R4与它们相连接的碳原子一起是C5-C12环烷基，
R5、R6、R7、R8和R9彼此独立地是氢、C1-C8烷基、C2-C8烯基、未取代的或被C1-C4烷基、C1-C4烷氧基或卤素取代的C5-C12芳基；C1-C4卤代烷基、氰基、硝基、卤素或-COOR10；和R7和R8一起还可以形成化学键，
R10是C1-C12烷基、C5-C12环烷基、C7-C9苯基烷基或苯基，
该方法包括：式II的化合物
其中R、R1、R2、R3和R4如上所述，与式III的化合物
其中R5、R6、R7、R8和R9如上所述，在含有膦配体的钯催化剂的存在下进行反应，其中存在溶剂，该溶剂是甲苯或丙酮。
2.按照权利要求1的方法，其中R1、R2、R3和R4是甲基。
3.按照权利要求1的方法，其中R5、R6、R7、R8和R9是氢。
4.按照权利要求1的方法，其中R是和
R11是与三嗪环相连接的氮。
5.按照权利要求1的方法，其中
R是
R1、R2、R3和R4是甲基，
R5、R6、R7、R8和R9是氢，和
R11是与三嗪环相连接的氮。
6.按照权利要求1的方法，其中相对于每单位式II的空间位阻的仲胺，以等摩尔至100倍过量的数量使用式III的化合物。
7.按照权利要求1的方法，其中催化剂是(四三苯基膦)钯。
8.按照权利要求1的方法，其中相对于每单位式II的空间位阻的仲胺，以0.01至30mo1％的数量使用催化剂。
9.按照权利要求1的方法，其中还存在碱。
10.按照权利要求1的方法，其中还存在二氧化碳或另一种惰性气体或其混合物。
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| PCT/EP2007/062321 WO2008061923A1 (en) | 2006-11-23 | 2007-11-14 | Process for the preparation of tertiary n-allyl sterically hindered amines |
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| US4014887A (en) * | 1972-10-21 | 1977-03-29 | Ciba-Geigy Corporation | Substituted piperidin-4-ols |
| US4141883A (en) * | 1975-05-28 | 1979-02-27 | Sankyo Company, Limited | Stabilization of synthetic polymers by penta-or-hexa-substituted 4-piperidinol derivatives |
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| JPS5848580B2 (ja) * | 1975-05-28 | 1983-10-29 | 三共株式会社 | ゴウセイコウブンシザイリヨウヨウアンテイザイ |
| DE3379050D1 (en) * | 1982-08-11 | 1989-03-02 | Ciba Geigy Ag | Process for the chemical bond between a stabilising compound and a polymer |
| IT1191804B (it) * | 1986-06-11 | 1988-03-23 | Enichem Sintesi | Procedimento per la preparazione di derivati n-allil-piperidinici |
| JPH0757743B2 (ja) * | 1987-12-23 | 1995-06-21 | 昭和電工株式会社 | アリル型アミンの製造法 |
| JPH04208233A (ja) * | 1990-11-30 | 1992-07-29 | Kuraray Co Ltd | アリリツクアルコールのアリル交換方法 |
| AU7216796A (en) * | 1995-10-12 | 1997-04-30 | Ciba-Geigy Ag | Thermally stable hindered amines as stabilizers |
| ITMI980366A1 (it) * | 1998-02-25 | 1999-08-25 | Ciba Spec Chem Spa | Preparazione di eteri amminici stericamente impediti |
| SG74700A1 (en) * | 1998-02-25 | 2000-08-22 | Ciba Sc Holding Ag | Preparation of sterically hindered amine ethers |
| HN2002000156A (es) * | 2001-07-06 | 2003-11-27 | Inc Agouron Pharmaceuticals | Derivados de benzamida tiazol y composiciones farmaceuticas para inhibir la proliferacion de celulas y metodos para su utilización. |
| JP4381055B2 (ja) * | 2003-08-29 | 2009-12-09 | 広栄化学工業株式会社 | アリルアミン類の製造方法 |
| US7595011B2 (en) * | 2004-07-12 | 2009-09-29 | Ciba Specialty Chemicals Corporation | Stabilized electrochromic media |
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| US4014887A (en) * | 1972-10-21 | 1977-03-29 | Ciba-Geigy Corporation | Substituted piperidin-4-ols |
| US4141883A (en) * | 1975-05-28 | 1979-02-27 | Sankyo Company, Limited | Stabilization of synthetic polymers by penta-or-hexa-substituted 4-piperidinol derivatives |
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| KR20090080964A (ko) | 2009-07-27 |
| ES2388886T3 (es) | 2012-10-19 |
| EP2084150A1 (en) | 2009-08-05 |
| TWI408134B (zh) | 2013-09-11 |
| CN101541787A (zh) | 2009-09-23 |
| US20100087639A1 (en) | 2010-04-08 |
| EP2084150B1 (en) | 2012-08-08 |
| KR101454703B1 (ko) | 2014-10-27 |
| US8217170B2 (en) | 2012-07-10 |
| JP2010510280A (ja) | 2010-04-02 |
| TW200902511A (en) | 2009-01-16 |
| JP5649822B2 (ja) | 2015-01-07 |
| WO2008061923A1 (en) | 2008-05-29 |
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