CN110746377B - 负载型金属催化合成1-取代的吡咯烷/哌啶衍生物的方法 - Google Patents
负载型金属催化合成1-取代的吡咯烷/哌啶衍生物的方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 34
- -1 1-substituted pyrrolidine Chemical class 0.000 title claims abstract description 27
- 150000003053 piperidines Chemical class 0.000 title claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 19
- 239000002184 metal Substances 0.000 title claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 title claims description 8
- 238000006555 catalytic reaction Methods 0.000 title claims description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 65
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 50
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 32
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 10
- 239000002808 molecular sieve Substances 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 claims description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 claims 5
- 229940043375 1,5-pentanediol Drugs 0.000 claims 4
- 150000003938 benzyl alcohols Chemical class 0.000 claims 2
- 230000032683 aging Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 67
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical group C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 abstract description 32
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000007363 ring formation reaction Methods 0.000 abstract description 6
- 238000011068 loading method Methods 0.000 abstract description 5
- 150000003235 pyrrolidines Chemical class 0.000 abstract description 3
- 238000007126 N-alkylation reaction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 48
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 17
- JSHASCFKOSDFHY-UHFFFAOYSA-N 1-butylpyrrolidine Chemical compound CCCCN1CCCC1 JSHASCFKOSDFHY-UHFFFAOYSA-N 0.000 description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 12
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 12
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- VTDIWMPYBAVEDY-UHFFFAOYSA-N 1-propylpiperidine Chemical compound CCCN1CCCCC1 VTDIWMPYBAVEDY-UHFFFAOYSA-N 0.000 description 6
- AXWLKJWVMMAXBD-UHFFFAOYSA-N 1-butylpiperidine Chemical compound CCCCN1CCCCC1 AXWLKJWVMMAXBD-UHFFFAOYSA-N 0.000 description 5
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- 150000001414 amino alcohols Chemical class 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 230000002431 foraging effect Effects 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- NZVZVGPYTICZBZ-UHFFFAOYSA-N 1-benzylpiperidine Chemical compound C=1C=CC=CC=1CN1CCCCC1 NZVZVGPYTICZBZ-UHFFFAOYSA-N 0.000 description 3
- ONQBOTKLCMXPOF-UHFFFAOYSA-N 1-ethylpyrrolidine Chemical compound CCN1CCCC1 ONQBOTKLCMXPOF-UHFFFAOYSA-N 0.000 description 3
- BBYSGWAYRRMWOW-UHFFFAOYSA-N 1-hexylpiperidine Chemical compound CCCCCCN1CCCCC1 BBYSGWAYRRMWOW-UHFFFAOYSA-N 0.000 description 3
- OUKZCQQNMWXMNE-UHFFFAOYSA-N 1-hexylpyrrolidine Chemical compound CCCCCCN1CCCC1 OUKZCQQNMWXMNE-UHFFFAOYSA-N 0.000 description 3
- NWRUFJHICAREBX-UHFFFAOYSA-N 1-pentylpyrrolidine Chemical compound CCCCCN1CCCC1 NWRUFJHICAREBX-UHFFFAOYSA-N 0.000 description 3
- HLNRRPIYRBBHSQ-UHFFFAOYSA-N 1-propylpyrrolidine Chemical compound CCCN1CCCC1 HLNRRPIYRBBHSQ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HTLZVHNRZJPSMI-UHFFFAOYSA-N N-ethylpiperidine Chemical compound CCN1CCCCC1 HTLZVHNRZJPSMI-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- CWEGCQIIDCZZED-UHFFFAOYSA-N 1-benzylpyrrolidine Chemical compound C=1C=CC=CC=1CN1CCCC1 CWEGCQIIDCZZED-UHFFFAOYSA-N 0.000 description 2
- IIYSNNBEZBAQCQ-UHFFFAOYSA-N 1-butylpyrrole Chemical compound CCCCN1C=CC=C1 IIYSNNBEZBAQCQ-UHFFFAOYSA-N 0.000 description 2
- LQWJONARYDIOSE-UHFFFAOYSA-N 1-pentylpiperidine Chemical compound CCCCCN1CCCCC1 LQWJONARYDIOSE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910018590 Ni(NO3)2-6H2O Inorganic materials 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003233 pyrroles Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 238000002156 mixing Methods 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
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
- C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Hydrogenated Pyridines (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明提供了一种负载型金属催化合成1‑取代的吡咯烷/哌啶衍生物的方法,以负载型金属为催化剂,1,4‑丁二醇/1,5‑戊二醇作为环化原料,醇作为N‑烷基化原料,与氨反应形成吡咯烷环/哌啶环,通过一步反应高选择性的合成1‑取代的吡咯烷/哌啶衍生物。其中负载型金属催化剂的活性组份为Cu、Ni、Pd/Ru,活性组分Cu和Ni的总负载量为载体的3~15wt.%,Pd/Ru的负载量为载体的0~1wt.%。本发明方法简单,成本低,环境友好,且1,4‑丁二醇/1,5‑戊二醇的转化率高,吡咯烷/哌啶衍生物的选择性高,是一条具有实际应用价值的生产路线。
Description
技术领域
本发明涉及一种1-取代的吡咯烷/哌啶衍生物的合成方法,尤其涉及一种负载型金属催化合成1-取代的吡咯烷/哌啶衍生物的方法,属于催化剂及化学合成技术领域。
背景技术
吡咯烷和哌啶衍生物在化学化工产领域非常重要的平台化学品,可以作为医药和有机中间体、农药、特种溶剂以及鎓类离子液体的原料等。
传统合成吡咯烷的方法包括1:四氢吡咯烷基化法,以四氢吡咯为原料,与醛类,醇类等反应合成吡咯烷衍生物,如【精细与专用化学品】,2004,24-25以甲醛为甲基化原料在甲酸介质中与四氢吡咯反应制备N-甲基吡咯烷,反应结束后加入盐酸,经蒸馏、过滤、NaOH中和得到产品,该路线中需要用大量的NaOH中和,产生无用的废盐,对环境污染严重;Journal of the American Chemical Society, 137(40), 12796-12799; 2015以卤代烷和四氢吡咯反应合成了一系列1-取代吡咯烷(从丙基到己基),该方法同样产生了卤化氢,需要以NaOH中和,且吡咯烷价格昂贵,此外,还有报道以醇类作为烷基化试剂和吡咯烷反应合成1-取代吡咯烷衍生物的方法,虽然路线较为绿色,产品收率比较高,但催化剂通常用到贵金属。2:加氢还原法,该路线以催化剂催化N-烷基吡咯烷酮、吡咯衍生物加氢还原制备1-取代吡咯烷衍生物,该路线虽反应条件较为温和,反应绿色,产品收率高,但该路线催化剂通常用到贵金属,且N-烷基吡咯烷酮、吡咯衍生物价格比较贵,限制了其工业化应用。3:胺醇脱水环化法,如Beilstein J. Org. Chem. 2017. 13: 329-337.报道了通过胺醇脱水环化合成吡咯烷衍生物的方法,可以高收率的获得目标产物,但胺醇作为原料本身价格昂贵,结构复杂,增加了原料成本。
传统合1-哌啶衍生物的方法包括1:哌啶烷基化法,该路线与吡咯烷烷基化方法类似,如Journal of Organic Chemistry, 70(6),2195-2199; 2005报道以醛类与哌啶合成1-取代哌啶衍生物;Catalysis Communications, 8(3), 576-582; 2007 以卤代烷和哌啶作为原料合成1-取代哌啶衍生物;Organic Letters, 15(2), 266-269; 2013以伯醇和哌啶合成1-取代哌啶衍生物等,可以高收率的获得目标产物,但该方法主要原料哌啶价格昂贵,卤代烷的使用对环境不够友好,且报道的催化剂多为贵金属催化剂等。2:加氢还原法:如Angewandte Chemie, International Edition, 52(8), 2231-2234; 2013报道了通过还原带有1-取代的哌啶酮衍生物获得哌啶的衍生物;中国专利CN102091638A和CN102093283A报道了通过吡啶衍生物加氢制备1-取代哌啶衍生物的方法,该方法虽然反应条件较为温和,产品收率也高,但该方法同样存在原料价格昂贵,需要用到贵金属催化剂等问题;3:胺醇脱水环化法,如Catalysis Science & Technology, 4(1),47-52; 2014报道了通过胺醇脱水环化合成一系列哌啶衍生物的方法,可以获得很高收率的目标产物,但胺醇作为原料本身价格昂贵,结构复杂,限制了该方法的工业化应用。
以1,4-丁二醇/1,5-戊二醇和伯胺胺化环化合成吡咯烷和哌啶衍生物是一条经济绿色的方法,但通常碳链较长伯胺活性高,在反应过程中容易相互脱氨不可避免的生成仲胺和叔胺,如Journal of Organometallic Chemistry 1989. 373: 343-352 报道了以1,4-丁二醇合成1-丁基吡咯烷,其收率仅有36%。副产物的大量生成降低了目标产物的收率,也给分离和提纯造成了困难。
发明内容
本发明的目的是提供一种负载型金属催化合成1-取代的吡咯烷/哌啶衍生物的方法。
本发明催化合成1-取代的吡咯烷/哌啶衍生物的方法,是以负载型金属作为催化剂,采用1,4-丁二醇/1,5-戊二醇、氨及醇为原料,在H2还原气氛下,于230~330ºC、初始压力2~4Mpa下反应1~8 h,一步制得1-取代吡咯烷/哌啶衍生物。其合成路线如下:
所述原料醇为C2-C8直链醇、侧链为直链的苯甲醇至苯己醇。
原料氨为20~80wt.%氨水溶液或氨气;原料1,4-丁二醇/1,5-戊二醇:氨:醇的摩尔比为1:1:1~1:3:3。
H2与1,4-丁二醇/1,5-戊二醇的摩尔比为0.3:1~0.6:1。
负载型金属催化剂的用量为1,4-丁二醇/1,5-戊二醇与醇总质量的5%~20% 。
所述的负载型金属催化剂,包括活性组分和催化剂载体;其中,活性组份为Cu、Ni和Pd/ Ru,且活性组分Cu和Ni的总负载量为催化剂载体质量的3~15%,且Cu和Ni的质量比为1:1;Pd/Ru的总负载量为催化剂载体质量的0~1%。催化剂载体为Al2O3、SiO2或ZSM-5分子筛。
负载型金属催化剂的制备,是将Cu、Ni及Pd/Ru金属的盐通过浸渍法负载在Al2O3、SiO2或ZSM-5分子筛上而得。具体为:是将Ni(NO3)2·6H2O、Cu(NO3) ·3H2O、氯钯酸铵/水合三氯化钌搅拌溶解于去离子水中,再缓慢加入催化剂载体,室温下充分搅拌混匀后静置老化1~3h,然后放入100~110℃烘箱中干燥10~12h;最后在马弗炉中于300~500℃下焙烧2-5h,得到负载型金属催化剂。
本发明与现有技术相比具有以下优势:以负载型金属为催化剂,1,4-丁二醇或1,5-戊二醇作为环化原料,醇作为N-烷基化原料,与氨反应形成吡咯烷环/哌啶环,通过一步反应高选择性的合成1-取代的吡咯烷/哌啶衍生物,大大简化了反应流程,节约了原料成本,且原料价廉易得,环境友好,提供了一条具有实际应用价值的生产路线。
具体实施方式
为了更好地理解本发明,下面通过具体实施例对本发明1-取代的吡咯烷/哌啶衍生物的方法作进一步进行阐述。
实施例1:1-丁基吡咯烷的制备
(1)催化剂3%Cu-3%Ni-0.2%Pd/ZSM-5的制备:称取27.8g Ni(NO3)2·6H2O、21.1gCu(NO3)2·3H2O和1g氯钯酸铵(含Pd 0.37g)加入3L烧杯中,添加56ml去离子水,然后在室温条件下搅拌溶解,再缓慢加入185g ZSM-5(NKF-5-80HW)分子筛,加料完成后置于室温条件下充分搅拌,静置老化3h,放入110ºC烘箱中干燥12h,干燥完成后置于马弗炉中500ºC焙烧3h,即得3%Cu-3%Ni-0.2%Pd/ZSM-5催化剂;
(2)1-丁基吡咯烷的制备:准确称量360g 1,4-丁二醇(BDO,4mol),328g 25wt.%氨水溶液(含4.8mol氨),356g正丁醇(4.8mol),72g 3%Cu-3%Ni-0.2%Pd/ZSM-5催化剂,于4L反应釜中,在4MPa H2氛围下反应,设置反应温度290ºC,反应4h后结束反应,BDO的转化率100%,1-丁基吡咯烷选择性为85%。
实施例2:1-乙基吡咯烷的制备
(1)催化剂3%Cu-3%Ni-0.2%Pd/ZSM-5的制备:同实施例1;
(2)1-乙基吡咯烷的制备:准确称量360g BDO(4mol),328g 25wt.%氨水溶液(含4.8mol氨),220g乙醇(4.8mol),58g 3%Cu-3%Ni-0.2%Pd/ZSM-5催化剂,于4L反应釜中,在4MPa H2氛围下反应,设置反应温度290ºC,反应4h后结束反应,BDO的转化率100%,1-乙基吡咯烷选择性为71%。
实施例3、1-丙基吡咯烷的制备
(1)催化剂3%Cu-3%Ni-0.2%Pd/ZSM-5的制备:同实施例1;
(2)1-丙基吡咯烷的制备:准确称量360g BDO(4mol),328g 25wt.%氨水溶液(含4.8mol氨),288g丙醇(4.8mol),65g 3%Cu-3%Ni-0.2%Pd/ZSM-5催化剂,于4L反应釜中,在4MPa H2氛围下反应,设置反应温度290ºC,反应4h后结束反应,BDO的转化率100%,1-丙基吡咯烷选择性为75%。
实施例4:1-戊基吡咯烷的制备
(1)催化剂3%Cu-3%Ni-0.2%Pd/ZSM-5的制备:同实施例1;
(2)1-戊基吡咯烷的制备:准确称量360g BDO(4mol),328g 25wt.%氨水溶液(含4.8mol氨),424g正戊醇(4.8mol),78g 3%Cu-3%Ni-0.2%Pd/ZSM-5催化剂,于4L反应釜中,在4MPa H2氛围下反应,设置反应温度290ºC,反应4h后结束反应,BDO的转化率100%,1-戊基吡咯烷选择性为73%。
实施例5:1-己基吡咯烷的制备
(1)催化剂3%Cu-3%Ni-0.2%Pd/ZSM-5的制备:同实施例1;
(2)1-己基吡咯烷的制备:准确称量360g BDO(4mol),328g 25wt.%氨水溶液(含4.8mol氨),488 g正己醇(4.8mol),85g 3%Cu-3%Ni-0.2%Pd/ZSM-5催化剂,于4L反应釜中,在4MPa H2氛围下反应,设置反应温度290ºC,反应4h后结束反应,BDO的转化率100%,1-己基吡咯烷选择性为71%。
实施例6:1-乙基哌啶的制备
(1)催化剂3%Cu-3%Ni-0.2%Pd/ZSM-5的制备:同实施例1;
(2)1-乙基哌啶的制备:准确称量416 g 1,5-戊二醇(PDO,4 mol),328g 25wt.%氨水溶液(含4.8mol氨),220g乙醇(4.8mol),63g3%Cu-3%Ni-0.2%Pd/ZSM-5催化剂,于4L反应釜中,在4MPa H2氛围下反应,设置反应温度290ºC,反应4h后结束反应,PDO的转化率100%,1-乙基哌啶选择性为78%。
实施例7:1-丙基哌啶的制备
(1)催化剂3%Cu-3%Ni-0.2%Pd/ZSM-5的制备:同实施例1;
(2)1-丙基哌啶的制备:准确称量416 g PDO(4 mol),328g 25wt.%氨水溶液(含4.8mol氨),288g丙醇(4.8mol),40g 3%Cu-3%Ni-0.2%Pd/ZSM-5催化剂,于4L反应釜中,在4MPa H2氛围下反应,设置反应温度290ºC,反应4h后结束反应,PDO的转化率100%,1-丙基哌啶选择性为75%。
实施例8:1-丁基哌啶的制备
(1)催化剂3%Cu-3%Ni-0.2%Pd/ZSM-5的制备:同实施例1;
(2)1-丁基哌啶的制备:准确称量准确称量416 g PDO(4 mol),328g 25wt.%氨水溶液(含4.8mol氨),356g正丁醇(4.8mol),77g 3%Cu-3%Ni-0.2%Pd/ZSM-5催化剂,于4L反应釜中,在4MPa H2氛围下反应,设置反应温度290ºC,反应4h后结束反应,PDO的转化率100%,1-丁基哌啶选择性为74%。
实施例9:1-戊基哌啶的制备
(2)1-戊基哌啶的制备:准确称量416 g PDO(4 mol),328g 25wt.%氨水溶液(含4.8mol氨)),424g正戊醇(4.8mol),84g 3%Cu-3%Ni-0.2%Pd/ZSM-5催化剂,于4L反应釜中,在4MPa H2氛围下反应,设置反应温度290ºC,反应4h后结束反应,PDO的转化率100%,1-戊基哌啶选择性为77%。
实施例10:1-己基哌啶的制备
(1)催化剂3%Cu-3%Ni-0.2%Pd/ZSM-5的制备:同实施例1;
(2)1-己基哌啶的制备:准确称量416 g PDO(4 mol),328g 25wt.%氨水溶液(含4.8mol氨),488g正己醇(4.8mol),90g 3%Cu-3%Ni-0.2%Pd/ZSM-5催化剂,于4L反应釜中,在4MPa H2氛围下反应,设置反应温度290ºC,反应4h后结束反应,PDO的转化率100%,1-己基哌啶选择性为71%。
实施例11:1-丁基吡咯烷的制备
(1)催化剂3%Cu-3%Ni-0.2%Ru/ZSM-5的制备:称取27.8g Ni(NO3)2•6H2O、21.1gCu(NO3) •3H2O和1g水合三氯化钌(含Ru 0.375g)加入3L烧杯中,添加56ml去离子水,然后在室温条件下搅拌溶解,再缓慢加入185g ZSM-5(NKF-5-80HW)分子筛,加料完成后置于室温条件下充分搅拌,静置老化3h,放入110ºC烘箱中干燥12h;干燥完成后置于马弗炉中500℃焙烧3h,得到催化剂3%Cu-3%Ni-0.2%Ru/ZSM-5;
(2)1-丁基吡咯烷的制备:准确称量准确称量360 g BDO(4 mol),328g 25wt.%氨水溶液(含4.8mol氨),356g正丁醇(4.8mol),72g 3%Cu-3%Ni-0.2%Ru/ZSM-5催化剂,于4L反应釜中,在4MPa H2氛围下反应,设置反应温度290ºC,反应4h后结束反应,BDO的转化率100%,1-丁基吡咯烷选择性为79%。
实施例12:1-苄基吡咯烷的制备
(1)催化剂3%Cu-3%Ni-0.2%Pd/ZSM-5的制备:同实施例1;
(2)1-苄基吡咯烷的制备:准确称量准确称量360 g BDO(4 mol),328g 25wt.%氨水溶液(含4.8mol氨),520g苯甲醇(4.8mol),94 g3%Cu-3%Ni-0.2%Pd/ZSM-5催化剂,于4L反应釜中,在4MPa H2氛围下反应,设置反应温度290ºC,反应4h后结束反应,BDO的转化率100%,1-苄基吡咯烷选择性为28%。
实施例13:1-苄基哌啶的制备
(1)催化剂3%Cu-3%Ni-0.2%Pd/ZSM-5的制备:同实施例1;
(2)1-苄基哌啶的制备:准确称量416 g PDO(4 mol),328g 25wt.%氨水溶液(含4.8mol氨),520g苯甲醇(4.8mol),94g 3%Cu-3%Ni-0.2%Pd/ZSM-5催化剂,于4L反应釜中,在4MPa H2氛围下反应,设置反应温度290ºC,反应4h后结束反应,PDO的转化率100%,1-苄基哌啶选择性为37%。
实施例14:1-丁基吡咯烷的制备
(1)催化剂3%Cu-3%Ni-0.2%Pd/ZSM-5的制备:同实施例1;
(2)1-丁基吡咯烷的制备:准确称量360 g BDO(4 mol),328g 25wt.%氨水溶液(含4.8mol氨),356g正丁醇(4.8mol),72g 3%Cu-3%Ni -0.2%Pd/ZSM-5催化剂,于4L反应釜中,在2MPa H2氛围下反应,设置反应温度290ºC,反应4h后结束反应,BDO的转化率100%,1-丁基吡咯烷选择性为74%。
实施例15:1-丁基吡咯烷的制备
(1)催化剂3%Cu-3%Ni/ZSM-5的制备:称取27.8g Ni(NO3)2·6H2O、21.1g Cu(NO3)·3H2O,加入3L烧杯中,添加56ml去离子水,然后在室温条件下搅拌溶解,再缓慢加入185g ZSM-5分子筛,加料完成后置于室温条件下充分搅拌,静置老化3h,放入110ºC烘箱中干燥12h;干燥完成后置于马弗炉中500℃焙烧3h,得到催化剂3%Cu-3%Ni /ZSM-5;
(2)1-丁基吡咯烷的制备:准确称量360 g BDO(4 mol),328g 25wt.%氨水溶液(含4.8mol氨),356 g正丁醇(4.8mol), 71.6g 3%Cu-3%Ni /ZSM-5催化剂,于4L反应釜中,在4MPa H2氛围下反应,设置反应温度290ºC,反应4h后结束反应,BDO的转化率100%,1-丁基吡咯烷选择性为54%。
实施例16:1-丁基吡咯烷的制备
(1)催化剂3%Cu-3%Ni-0.2%Pd/ZSM-5的制备:同实施例1;
(2)1-丁基吡咯烷的制备:准确称量360 g BDO(4 mol),328g 25wt.%氨水溶液(含4.8mol氨),592 g正丁醇(8mol),62g 3%Cu-3%Ni-0.2%Pd/ZSM-5催化剂,于4L反应釜中,在4MPa H2氛围下反应,设置反应温度300ºC,反应4h后结束反应,BDO的转化率100%,1-丁基吡咯烷选择性为84%。
上述各实施例中,1,4-丁二醇/1,5-戊二醇的转化率及1-取代的吡咯烷/哌啶衍生物的选择性分析测试条件:反应后所得产物加入内标物联苯,经内标法定量分析,采用Agilent Technologies 7890A气相色谱系统定量分析。色谱条件为:色谱柱30 m × 0.25mm × 0.33 μm的毛细管,氢火焰离子化(FID)检测器。定性分析利用AgilentTechnologies 7890B-5977A GC-MS完成,色谱条件为:色谱柱30 m × 0.25 mm × 0.25 μm的毛细管,EI离子源,长效高能量电子倍增器检测器。
Claims (6)
1.负载型金属催化合成1-取代的吡咯烷/哌啶衍生物的方法,是以负载型金属作为催化剂,采用1,4-丁二醇/1,5-戊二醇、氨及醇为原料,在H2还原气氛下,于230~330ºC、初始压力2~4Mpa下反应1~8 h,一步制得1-取代吡咯烷/哌啶衍生物;
所述的负载型金属催化剂包括活性组分和催化剂载体,其中活性组份为Cu、Ni和Pd/Ru,且活性组分Cu和Ni的总负载量为催化剂载体质量的3~15%,且Cu和Ni的质量比为1:1;Pd/Ru的总负载量为催化剂载体质量的0.2~1%;催化剂载体为Al2O3、SiO2或ZSM-5分子筛;
所述原料醇为C2-C8直链醇、侧链为直链的苯甲醇至苯己醇。
2.如权利要求1所述负载型金属催化合成1-取代的吡咯烷/哌啶衍生物的方法,其特征在于:原料氨为20~80wt.%氨水溶液或氨气。
3.如权利要求1所述负载型金属催化合成1-取代的吡咯烷/哌啶衍生物的方法,其特征在于:原料1,4-丁二醇/1,5-戊二醇:氨:醇的摩尔比为1:1:1~1:3:3。
4.如权利要求1所述负载型金属催化合成1-取代的吡咯烷/哌啶衍生物的方法,其特征在于:H2与1,4-丁二醇/1,5-戊二醇的摩尔比为0.3:1~0.6:1。
5.如权利要求1所述负载型金属催化合成1-取代的吡咯烷/哌啶衍生物的方法,其特征在于:负载型金属催化剂的用量为1,4-丁二醇/1,5-戊二醇与醇总质量的5%~20% 。
6.如权利要求1所述负载型金属催化合成1-取代的吡咯烷/哌啶衍生物的方法,其特征在于:负载型金属催化剂的制备,是将Ni(NO3)2·6H2O、Cu(NO3)2·3H2O、氯钯酸铵/水合三氯化钌搅拌溶解于去离子水中,再缓慢加入催化剂载体,室温下充分搅拌混匀后静置老化1~3h,然后放入100~110℃烘箱中干燥10~12h;最后在马弗炉中于300~500℃下焙烧2~5h,得到负载型金属催化剂。
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