CN111848931B - 一类含有吡啶基团的多孔有机聚合物的制备方法和应用 - Google Patents
一类含有吡啶基团的多孔有机聚合物的制备方法和应用 Download PDFInfo
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229920000620 organic polymer Polymers 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 33
- 238000006170 formylation reaction Methods 0.000 claims abstract description 21
- 150000001412 amines Chemical class 0.000 claims abstract description 20
- -1 transition metal salt Chemical class 0.000 claims abstract description 12
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- 229910019891 RuCl3 Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 53
- 239000000758 substrate Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 16
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 230000021235 carbamoylation Effects 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 229940125904 compound 1 Drugs 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 150000003141 primary amines Chemical group 0.000 claims description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 3
- 150000003335 secondary amines Chemical class 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- LAXRNWSASWOFOT-UHFFFAOYSA-J (cymene)ruthenium dichloride dimer Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Ru+2].[Ru+2].CC(C)C1=CC=C(C)C=C1.CC(C)C1=CC=C(C)C=C1 LAXRNWSASWOFOT-UHFFFAOYSA-J 0.000 claims description 2
- WWRCMNKATXZARA-UHFFFAOYSA-N 1-Isopropyl-2-methylbenzene Chemical compound CC(C)C1=CC=CC=C1C WWRCMNKATXZARA-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- MLIYPCQSOXNTLJ-UHFFFAOYSA-N carbon monoxide;ruthenium dihydride;triphenylphosphane Chemical compound [RuH2].[O+]#[C-].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 MLIYPCQSOXNTLJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940125782 compound 2 Drugs 0.000 claims description 2
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 125000002560 nitrile group Chemical group 0.000 claims description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N p-methylisopropylbenzene Natural products CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000000536 complexating effect Effects 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 22
- 239000007789 gas Substances 0.000 description 22
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 238000011049 filling Methods 0.000 description 12
- 239000005457 ice water Substances 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 238000012512 characterization method Methods 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 11
- 239000006228 supernatant Substances 0.000 description 11
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 8
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IIFVWLUQBAIPMJ-UHFFFAOYSA-N (4-fluorophenyl)methanamine Chemical compound NCC1=CC=C(F)C=C1 IIFVWLUQBAIPMJ-UHFFFAOYSA-N 0.000 description 2
- ZXWCKKSSCIFVBT-UHFFFAOYSA-N 1-(3-fluorophenyl)-n-methylmethanamine Chemical compound CNCC1=CC=CC(F)=C1 ZXWCKKSSCIFVBT-UHFFFAOYSA-N 0.000 description 2
- AIJFPNKGGAPZFJ-UHFFFAOYSA-N 1-(4-methoxyphenyl)-n-methylmethanamine Chemical compound CNCC1=CC=C(OC)C=C1 AIJFPNKGGAPZFJ-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- YDFFIGRIWDSNOZ-UHFFFAOYSA-N n-methyl-1-(4-methylphenyl)methanamine Chemical compound CNCC1=CC=C(C)C=C1 YDFFIGRIWDSNOZ-UHFFFAOYSA-N 0.000 description 2
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- DJLBVUYUIACDIU-UHFFFAOYSA-N tris(4-ethenylphenyl)phosphane Chemical compound C1=CC(C=C)=CC=C1P(C=1C=CC(C=C)=CC=1)C1=CC=C(C=C)C=C1 DJLBVUYUIACDIU-UHFFFAOYSA-N 0.000 description 2
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 150000003948 formamides Chemical class 0.000 description 1
- 230000022244 formylation Effects 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C07D295/16—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 acylated on ring nitrogen atoms
- C07D295/18—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 acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
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Abstract
本发明公开了一类含有吡啶基团的多孔有机聚合物的制备方法和应用。所述聚合物Ⅰ具有如下通式：
上述聚合物是通过将
与
进行共聚得到。本发明所提供的含有吡啶基团的多孔有机聚合物与过渡金属盐RuCl3络合形成的催化剂，可用于催化胺的氮甲酰化反应，具有高催化速率、好的收率和循环性等优点。
Description
技术领域
本发明涉及一类含有吡啶基团的多孔有机聚合物及其制备方法和应用。具体说，是涉及一类含有吡啶和三苯基膦配体的多孔聚合物及其制备方法，该聚合物负载钌催化剂可以高效催化胺的氮甲酰化反应，属于有机化学技术领域。
技术背景
氮甲酰化反应是指胺和酰化试剂反应生成甲酰胺的过程。甲酰胺类化合物不仅可以用于溶剂和反应试剂，而且也可以用作催化剂。CO2/H2作为酰基化试剂，过渡金属催化胺的酰化反应为合成甲酰胺类化合物提供了一类绿色的合成方法。相比较均相催化体系的氮甲酰化反应，非均相催化体系的氮甲酰化反应有更大的研究价值。然而在非均相催化体系的氮甲酰化反应中，合成具有多孔有机聚合物作为配体，并将金属负载在多孔有机聚合物中催化氮甲酰化反应的研究相对较少。多孔有机聚合物负载金属催化剂作为一种有机配体载体，具有多孔性、比表面积高、化学性质稳定和便于回收等优点。发展至今，非均相催化氮甲酰化反应仍然有很多困难需要克服：第一，催化剂的活性较低；第二，催化剂的循环回收问题很难解决。因此基于以上问题，本专利成功开发了一类具有吡啶基团的多孔有机聚合物，该聚合物负载钌构建的非均相催化剂在胺的氮甲酰化反应中的表现出高的催化速率、好的收率和循环性，具有实用价值。
发明内容
本发明的目的是提供一类含有吡啶基团的多孔有机聚合物及其制备方法和应用，为非均相催化胺的氮甲酰化增添一类新催化剂。
本发明所述的含有吡啶基团的多孔有机聚合物I，其具有如下结构通式：
上述结构通式中：R1、R2、R3、R4、R5、R6分别独立选自氢、磺酸基、卤素、腈基、胺基、C1～C12的烷烃基、C1～C10的烷氧基。
其中：m与n的比例为1:1～10:1。
一种制备上述具有吡啶基团的多孔有机聚合物的的制备方法，将通式1中化合物1与化合物2进行聚合反应，得到聚合物I，反应通式如下所示：
所述反应通式1中，化合物1由4-溴芳基乙烯与三氯化磷反应得到，反应通式如下所示：
本发明所述的含有吡啶基团的多孔有机聚合物是一种应用，用于催化胺的氮甲酰化反应。
作为一种优选方案，首先使所述具有吡啶和三苯基膦基团的多孔有机聚合物与过渡金属盐形成催化剂，然后用于催化胺的氮甲酰化反应。
作为进一步优选方案，上述催化剂的制备包括如下步骤：在惰性气体下，将所述含有吡啶基团的多孔有机聚合物与过渡金属盐加入有机溶剂中，在0～100℃搅拌反应0.1～24小时，除去溶剂，得到聚合物I/金属盐催化剂。
作为更进一步优选方案，所述具有吡啶基团的多孔有机聚合物与所述过渡金属盐的质量比为1∶1～50∶1，以5∶1～20∶1最佳。
作为更进一步优选方案，所述过渡金属盐为Ru。
作为更进一步优选方案，所述Ru盐为RuCl3,[RuCl2(p-cymene)]2,RuH2(CO)(PPh3)3,RuCl2(PPh3)3中的一种或多种,cymene代表甲基异丙苯。
作为更进一步优选方案，所述惰性气氛为氩气氛或氮气氛；所述有机溶剂选自苯、甲苯、二甲苯、三甲苯、乙醚、四氢呋喃、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、甲基叔丁基醚、乙二醇二甲醚、氯仿、二氯甲烷。
作为进一步优选方案，在惰性气氛下，向含有催化剂的反应釜中加入胺类底物、CO2和H2，在0～200℃条件下进行氮甲酰化反应；所述胺类底物为伯胺和仲胺；所述胺类底物与所述催化剂中Ru的摩尔比为100∶1～1000∶1，CO2压力为5～50个大气压，H2压力为5～50个大气压。
作为更进一步优选方案，所述胺类底物与所述催化剂(基于Ru)的摩尔比为200∶1～400∶1，CO2压力为10～30个大气压，H2压力为10～30个大气压；所述胺类底物为伯胺和仲胺。
作为更进一步优选方案，所述惰性气氛为氩气氛或氮气氛。
作为进一步优选方案，所述含有膦配体的多孔有机聚合物选自如下结构：
与现有技术相比，本发明具有如下显著效果：
1.本发明提供的含有吡啶基团的多孔有机聚合物负载钌催化剂，用于胺的氮甲酰化反应，均具有高催化活性和循环性。
2.本发明提供的含有吡啶基团的多孔有机聚合物负载钌催化剂的制备方法简单、反应条件温和、收率高，适于规模化生产，具有实用价值。
具体实施方式
下面结合实施例对本发明作进一步详细、完整地说明。
实施例1
下述实施例中所用三(4-乙烯基苯基)膦通过如下方法制备而得，具体为：
三(4-乙烯基苯基)膦
的制备
将镁(160mg,1.2mmol)切成小片置于烘干过并连有恒压滴液漏斗的三口烧瓶中，加入碘一颗，将反应体系密闭并置换成氮气体系，保证体系中无水无氧。恒压滴液漏斗中加入4-溴苯乙烯(0.7mL,1mmol)，加入无水四氢呋喃20mL。将恒压滴液漏斗中的混合液体缓慢滴加到烧瓶中，加热搅拌1个小时。将反应体系转至冰水浴中，用注射器向其中缓慢加入三氯化磷(0.15mL,0.3mmol)，搅拌过夜。搅拌过夜后加入饱和的氯化铵水溶液并用乙酸乙酯萃取，用分液漏斗分出有机相，加无水硫酸镁除水，粗品进一步经柱层析得到无色油状液体。核磁氢谱表征数据：1H NMR(CDCl3,500MHz):δ7.38(d,J＝10.0Hz,6H),7.29-7.26(m,6H),6.71(dd,J＝20.0,10.0Hz,3H),5.78(d,J＝20.0Hz,3H),5.28(d,J＝10.0Hz,3H)ppm.
实施例2
在氮气气氛下，向50mL的旋塞瓶中分别加入无水四氢呋喃(10.0mL)，共聚单元
(570.0mg,1.68mol)和
(35.3mg,0.34mmol)，最后加入5.0mg的引发剂AIBN。室温下搅拌10min后，在100℃下反应24h，产物经离心分离，四氢呋喃洗涤(3×6mL)旋蒸后得淡黄色的固体(590.0mg)。
实施例3
如下具有吡啶基团的多孔有机聚合物I负载钌催化剂Rh/I的合成
在氮气气氛下，向100mL的Schlenk管里分别加入
(500.0mg)，RuCl3(71.8mg)和无水四氢呋喃(8mL)。在室温下搅拌24h后，用无水甲苯洗涤反应产物后离心分离，如此离心洗涤三次。最后，减压旋蒸除去甲苯，再用油泵抽3h，得到催化剂Rh/I(570mg)。
实施例4
催化剂Rh/I催化吗啉(底物：催化剂＝222)的氮甲酰化反应
在手套箱中，向反应釜中加入催化剂Rh/I(16.5mg)、N-甲基吡咯烷酮(1.0mL)、吗啉(87μL，1mmol)和癸烷(10μL,0.05mmol)。然后充入CO2置换釜内氮气三次，再充入CO2(20atm)和H2(20atm)，油浴100℃下搅拌反应24h。反应完成后，用冰水浴冷却反应釜至室温，缓慢放掉气体，离心后上清液后测气相，收率为93％。核磁氢谱表征数据：1H NMR(500MHz,CDCl3)：δ7.84(s,1H),3.49(t,J＝4.8Hz,2H),3.44(t,J＝4.8Hz,2H),3.35(t,J＝4.8Hz,2H),3.21(t,J＝4.8Hz,2H).
实施例5
催化剂Rh/I催化吡咯烷(底物：催化剂＝222)的氮甲酰化反应
在手套箱中，向反应釜中加入催化剂Rh/I(16.5mg)、N-甲基吡咯烷酮(1.0mL)、吡咯烷(82μL，1mmol)和癸烷(10μL,0.05mmol)。然后充入CO2置换釜内氮气三次，再充入CO2(20atm)和H2(20atm)，油浴100℃下搅拌反应24h。反应完成后，用冰水浴冷却反应釜至室温，缓慢放掉气体，离心后上清液后测气相，收率为99％。核磁氢谱表征数据：1H NMR(500MHz,CDCl3)：δ8.24(s,1H),3.48(s,2H),3.41(s,2H),1.90(s,4H).
实施例6
催化剂Rh/I催化哌啶(底物：催化剂＝222)的氮甲酰化反应
在手套箱中，向反应釜中加入催化剂Rh/I(16.5mg)、N-甲基吡咯烷酮(1.0mL)、哌啶(91μL，1mmol)和癸烷(10μL,0.05mmol)。然后充入CO2置换釜内氮气三次，再充入CO2(20atm)和H2(20atm)，油浴100℃下搅拌反应24h。反应完成后，用冰水浴冷却反应釜至室温，缓慢放掉气体，离心后上清液后测气相，收率为99％。核磁氢谱表征数据：1H NMR(CDCl3,500MHz):δ7.87(s,1H),3.35(t,J＝5.0Hz),3.19(t,J＝5.0Hz,2H),1.59-1.54(m,2H),1.48-1.39(m,4H).
实施例7
催化剂Rh/I催化二正丁胺(底物：催化剂＝222)的氮甲酰化反应
在手套箱中，向反应釜中加入催化剂Rh/I(16.5mg)、N-甲基吡咯烷酮(1.0mL)、二正丁胺(168μL，1mmol)和癸烷(10μL,0.05mmol)。然后充入CO2置换釜内氮气三次，再充入CO2(20atm)和H2(20atm)，油浴100℃下搅拌反应24h。反应完成后，用冰水浴冷却反应釜至室温，缓慢放掉气体，离心后上清液后测气相，收率为68％。核磁氢谱表征数据：1H NMR(500MHz,CDCl3)：δ8.00(s,1H),3.24(t,J＝7.5Hz,2H),3.16(t,J＝7.5Hz,2H),1.48-1.47(m,4H),1.29-1.26(m,4H),0.91-0.87(m,6H).
实施例8
催化剂Rh/I催化N-甲基苄胺(底物：催化剂＝222)的氮甲酰化反应
在手套箱中，向反应釜中加入催化剂Rh/I(16.5mg)、N-甲基吡咯烷酮(1.0mL)、N-甲基苄胺(129μL，1mmol)和癸烷(10μL,0.05mmol)。然后充入CO2置换釜内氮气三次，再充入CO2(20atm)和H2(20atm)，油浴100℃下搅拌反应24h。反应完成后，用冰水浴冷却反应釜至室温，缓慢放掉气体，离心后上清液后测气相，收率为95％。核磁氢谱表征数据：1H NMR(500MHz,CDCl3)：δ8.21(major rotamer,s,0.57H),8.09(minor rotamer,s,0.42H),7.30-7.12(m,5H),4.45(minor rotamer,s,0.89H),4.32(major rotamer,s,1.19H),2.77(minorrotamer,s,1.31H),2.71(major rotamer,s,1.69H).
实施例9
催化剂Rh/I催化N-甲基-4-甲氧基苄胺(底物：催化剂＝222)的氮甲酰化反应在手套箱中，向反应釜中加入催化剂Rh/I(16.5mg)、N-甲基吡咯烷酮(1.0mL)、N-甲基-4-甲氧基苄胺(150μL，1mmol)和癸烷(10μL,0.05mmol)。然后充入CO2置换釜内氮气三次，再充入CO2(20atm)和H2(20atm)，油浴100℃下搅拌反应24h。反应完成后，用冰水浴冷却反应釜至室温，缓慢放掉气体，离心后上清液后测气相，收率为96％。核磁氢谱表征数据：1H NMR(500MHz,CDCl3):δ8.19(major rotamer,s,0.58H),8.05(minor rotamer,s,0.40H),7.11(minor rotamer,d,J＝8.5Hz,0.82H),7.05(major rotamer,d,J＝8.5Hz,1.17H),6.83-6.78(m,2.00H),4.38(minor rotamer,s,0.83H),4.25(major rotamer,s,1.18H),3.73(major rotamer,s,1.67H),3.72(minor rotamer,s,1.32H),2.75(minor rotamer,s,1.28H),2.68(major rotamer,s,1.72H).
实施例10
催化剂Rh/I催化N-甲基-4-甲基苄胺(底物：催化剂＝222)的氮甲酰化反应
在手套箱中，向反应釜中加入催化剂Rh/I(16.5mg)、N-甲基吡咯烷酮(1.0mL)、N-甲基-4-甲基苄胺(147μL，1mmol)和癸烷(10μL,0.05mmol)。然后充入CO2置换釜内氮气三次，再充入CO2(20atm)和H2(20atm)，油浴100℃下搅拌反应24h。反应完成后，用冰水浴冷却反应釜至室温，缓慢放掉气体，离心后上清液后测气相，收率为92％。核磁氢谱表征数据：1HNMR(CDCl3,500MHz):δ8.26(major rotamer,s,0.58H),8.13(minor rotamer,s,0.40H),7.17-7.07(m,4H),4.47(minor rotamer,s,0.83H),4.34(major rotamer,s,1.18H),2.82(minor rotamer,s,1.25H),2.76(major rotamer,s,1.75H),2.34(major rotamer,s,1.70H),2.32(minor rotamer,s,1.29H).
实施例11
催化剂Rh/I催化N-甲基-3-氟苄胺(底物：催化剂＝222)的氮甲酰化反应
在手套箱中，向反应釜中加入催化剂Rh/I(16.5mg)、N-甲基吡咯烷酮(1.0mL)、N-甲基-3-氟苄胺(136μL，1mmol)和癸烷(10μL,0.05mmol)。然后充入CO2置换釜内氮气三次，再充入CO2(20atm)和H2(20atm)，油浴100℃下搅拌反应24h。反应完成后，用冰水浴冷却反应釜至室温，缓慢放掉气体，离心后上清液后测气相，收率为97％。核磁氢谱表征数据：1H NMR(500MHz,CDCl3)：δ8.20(major rotamer,s,0.49H),8.10(minor rotamer,s,0.46H),7.30-7.21(m,1H),6.97-6.83(m,3H),4.44(minor rotamer,s,0.99H),4.32(major rotamer,s,1.03H),2.80(minor rotamer,s,1.47H),2.73(major rotamer,s,1.49H).
实施例12
催化剂Rh/I催化苄胺(底物：催化剂＝222)的氮甲酰化反应
在手套箱中，向反应釜中加入催化剂Rh/I(16.5mg)、N-甲基吡咯烷酮(1.0mL)、苄胺(109μL，1mmol)和癸烷(10μL,0.05mmol)。然后充入CO2置换釜内氮气三次，再充入CO2(20atm)和H2(20atm)，油浴100℃下搅拌反应24h。反应完成后，用冰水浴冷却反应釜至室温，缓慢放掉气体，离心后上清液后测气相，收率为72％。核磁氢谱表征数据：1H NMR(500MHz,CDCl3)δ8.19(major rotamer,s,0.82H),8.12(minor rotamer,d,J＝12.0Hz,0.17H),7.29-7.19(m,5H),5.85(br,1H),4.42(major rotamer,d,J＝6.0Hz,1.68H),4.34(minor rotamer,d,J＝6.5Hz,0.29H).
实施例13
催化剂Rh/I催化4-氟苄胺(底物：催化剂＝222)的氮甲酰化反应
在手套箱中，向反应釜中加入催化剂Rh/I(16.5mg)、N-甲基吡咯烷酮(1.0mL)、4-氟苄胺(114μL，1mmol)和癸烷(10μL,0.05mmol)。然后充入CO2置换釜内氮气三次，再充入CO2(20atm)和H2(20atm)，油浴100℃下搅拌反应24h。反应完成后，用冰水浴冷却反应釜至室温，缓慢放掉气体，离心后上清液后测气相，收率为75％。核磁氢谱表征数据：1H NMR(500MHz,CDCl3)：δ8.17(major rotamer,s,0.84H),8.14(minor rotamer,d,J＝12.0Hz,0.16H),7.20-7.17(m,2H),6.96-6.93(m,2H),5.97(br,1H),4.37(major rotamer,d,J＝6.0Hz,1.65H),4.31(minor rotamer,d,J＝6.5Hz,0.29H).
实施例14
催化剂Rh/I催化吗啉(底物：催化剂＝222)的氮甲酰化反应循环测试。
在手套箱中，向反应釜中加入催化剂Rh/I(40mg)、N-甲基吡咯烷酮(1.0mL)、吗啉(210μL，2.42mmol)和癸烷(10μL,0.05mmol)。然后充入CO2置换釜内氮气三次，再充入CO2(20atm)和H2(20atm)，油浴100℃下搅拌反应24h。反应完成后，用冰水浴冷却反应釜至室温，缓慢放掉气体，离心后上清液后测气相。催化剂用水洗3次，旋干水并真空干燥后以同样的反应条件循环8次。具体测试数据如下：
以上实施例仅用以说明本发明的技术方案，而非对其进行限制；尽管参照前述实施例对本发明进行了详细的说明，对于本领域的普通技术人员来说，依然可以对前述实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或替换，并不使相应技术方案的本质脱离本发明所要求保护的技术方案的精神和范围。
Claims (11)
1.一类含有吡啶基团的多孔有机聚合物，具有如下结构通式I：
上述通式中：R1、R2、R3、R4、R5、R6分别独立选自氢、磺酸基、卤素、腈基、胺基、C1～C12的烷烃基、C1～C10的烷氧基；
反应通式如下所示：
其中：m与n的比例为1:1～10:1。
2.一种权利要求1所述的含有吡啶基团的多孔有机聚合物的制备方法，其特征在于：将化合物1与化合物2进行聚合反应，得到聚合物I，反应通式如下所示：
上述通式中的R1、R2、R3、R4、R5、R6的含义均同权利要求1中所述。
3.一种根据权利要求1所述的含有吡啶基团的多孔有机聚合物的应用，其特征在于：用于催化胺的氮甲酰化反应。
4.根据权利要求3所述的应用，其特征在于：首先使用所述的含吡啶基团的多孔有机聚合物与过渡金属盐形成催化剂，然后用于催化胺的氮甲酰化反应。
5.根据权利要求4所述的应用，其特征在于，所述含有吡啶基团的多孔有机聚合物选自如下结构：
6.根据权利要求4所述的应用，其特征在于，所述催化剂的制备包括如下步骤：在惰性气体下，将所述含有吡啶基团的多孔有机聚合物与过渡金属盐加入有机溶剂中，在0～100℃搅拌反应0.1～20小时，除去溶剂，得到聚合物I/金属盐催化剂。
7.根据权利要求6所述的应用，其特征在于：所述含有吡啶基团的有机聚合物与所述过渡金属盐的质量比为1:1～50:1。
8.根据权利要求6所述的应用，其特征在于：所述惰性气氛为氩气氛或氮气氛；所述有机溶剂选自苯、甲苯、二甲苯、三甲苯、乙醚、四氢呋喃、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、甲基叔丁基醚、乙二醇二甲醚、氯仿、二氯甲烷。
9.根据权利要求4所述的应用，其特征在于：所述过渡金属盐为Ru盐。
10.根据权利要求9所述的应用，其特征在于：所述Ru盐为RuCl3,[RuCl2(p-cymene)]2,RuH2(CO)(PPh3)3,RuCl2(PPh3)3中的一种或多种,cymene代表甲基异丙苯。
11.根据权利要求4所述的应用，其特征在于：将所述催化剂用于催化胺的氮甲酰化反应的操作如下：在惰性气氛下，向含有催化剂的反应釜中加入胺类底物、CO2和H2，在0～200℃条件下进行氮甲酰化反应；所述胺类底物为伯胺和仲胺；所述过渡金属盐为Ru盐；所述胺类底物与所述催化剂中Ru的摩尔比为100:1～10000:1，CO2压力为5～50大气压，H2压力为5～50大气压。
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