CN114437143B - 一种吡啶基桥联双四唑廉价金属配合物及其制备和应用 - Google Patents
一种吡啶基桥联双四唑廉价金属配合物及其制备和应用 Download PDFInfo
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- 125000004076 pyridyl group Chemical group 0.000 title claims abstract description 53
- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 23
- 150000005309 metal halides Chemical class 0.000 claims abstract description 23
- 150000002576 ketones Chemical class 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 238000009901 transfer hydrogenation reaction Methods 0.000 claims abstract description 10
- 238000011911 α-alkylation Methods 0.000 claims abstract description 8
- 229940125782 compound 2 Drugs 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000460 chlorine Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052801 chlorine Chemical group 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000002541 furyl group Chemical group 0.000 claims description 6
- 125000001544 thienyl group Chemical group 0.000 claims description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000001308 synthesis method Methods 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 229910052740 iodine Chemical group 0.000 claims description 4
- 239000011630 iodine Chemical group 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 3
- -1 bitetrazole compound Chemical class 0.000 abstract description 11
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- QGGZBXOADPVUPN-UHFFFAOYSA-N dihydrochalcone Chemical compound C=1C=CC=CC=1C(=O)CCC1=CC=CC=C1 QGGZBXOADPVUPN-UHFFFAOYSA-N 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000004896 high resolution mass spectrometry Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YTNLBRCAVHCUPD-UHFFFAOYSA-N 5-(1$l^{2},2,3,4-tetrazol-5-yl)-1$l^{2},2,3,4-tetrazole Chemical compound [N]1N=NN=C1C1=NN=N[N]1 YTNLBRCAVHCUPD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 125000003107 substituted aryl group Chemical group 0.000 description 2
- 150000003536 tetrazoles Chemical group 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- QKLXBIHSGMPUQS-FGZHOGPDSA-M (3r,5r)-7-[4-(4-fluorophenyl)-2,5-dimethyl-1-phenylpyrrol-3-yl]-3,5-dihydroxyheptanoate Chemical compound CC1=C(CC[C@@H](O)C[C@@H](O)CC([O-])=O)C(C=2C=CC(F)=CC=2)=C(C)N1C1=CC=CC=C1 QKLXBIHSGMPUQS-FGZHOGPDSA-M 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- YLEIFZAVNWDOBM-ZTNXSLBXSA-N ac1l9hc7 Chemical compound C([C@H]12)C[C@@H](C([C@@H](O)CC3)(C)C)[C@@]43C[C@@]14CC[C@@]1(C)[C@@]2(C)C[C@@H]2O[C@]3(O)[C@H](O)C(C)(C)O[C@@H]3[C@@H](C)[C@H]12 YLEIFZAVNWDOBM-ZTNXSLBXSA-N 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- SRVFFFJZQVENJC-IHRRRGAJSA-N aloxistatin Chemical compound CCOC(=O)[C@H]1O[C@@H]1C(=O)N[C@@H](CC(C)C)C(=O)NCCC(C)C SRVFFFJZQVENJC-IHRRRGAJSA-N 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000013212 metal-organic material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical class [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 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
- 150000003303 ruthenium Chemical class 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
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- B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
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Abstract
本发明公开了一种吡啶基桥联双四唑廉价金属配合物及其制备和应用。以吡啶基桥联双四唑化合物与廉价金属卤化物在有机溶剂中发生配位反应，反应结束后经简单后处理，得到的金属配合物可用于催化酮的转移氢化或酮的α‑烷基化反应。本发明具有操作简便、反应条件温和、合成效率高等优点。
Description
技术领域
本发明涉及一种吡啶基桥联双四唑廉价金属配合物及其制备和应用，具体涉及以吡啶基桥联双四唑化合物与廉价金属卤化物在有机溶剂中发生配位反应，合成具有较高催化活性的金属配合物。
技术背景
氮杂环过渡金属配合物通常具有较高的催化活性，因而在配位化学、有机合成及均相催化等领域受到了越来越多的关注。吡啶基骨架三齿配体具有良好的配位能力，可以与过渡金属形成稳定的钳形配合物，因此在高活性配合物催化剂的研究中得到了广泛应用。基于吡啶基骨架的过渡金属配合物可用于高效催化转移氢化、交叉偶联及借氢策略反应等。如余正坤研究组报导了一系列吡啶基三齿配体及其钌配合物，在催化酮的转移氢化反应中表现出了优异的催化活性。
四唑化合物及其衍生物具有含氮量高、生成焓高及稳定性好等特点，在生物化学、农业、功能材料学及配位化学等方面都有着广泛的应用。吡啶基桥联双四唑化合物即保留了四唑基团，又具有含氮三齿配体独特的钳形结构，可以用做金属有机材料、高效稀土金属萃取剂及合成高活性过渡金属配合物催化剂等。如吡啶基双四唑化合物可通过自组装技术用于合成发光材料(Chem.Eur.J.2013,19,3477-3482)；该配体还可以用作次锕系金属的萃取剂，有效分离锕系-镧系元素An(III)/Ln(III)(Sci.China Chem.2012,55,1732-1738)；吡啶基桥联双四唑钌配合物还可以很好的催化酮的转移氢化反应(Chin.J.Catal.2018,39,327-333)。
常见的过渡金属配合物催化剂通常会使用钌、铑、铱等贵金属。与这些金属相比，廉价金属具有含量丰富、价格低廉、毒性小、对环境危害小等优点。将廉价金属卤化物与吡啶基桥联双四唑配体相结合制备相应的金属配合物催化剂符合绿色化学的理念，已成为科学工作者研究的重点和难点。
发明内容
本发明的目的在于提供一种吡啶基桥联双四唑廉价金属配合物及其制备和应用，是一种操作简便、反应条件温和、高收率的制备吡啶基桥联双四唑廉价金属配合物的方法。制备得到的金属配合物性质稳定，对空气不敏感，易于保存，并可用于催化酮的转移氢化或酮的α-烷基化反应。
为了实现上述目的，本发明的技术方案如下：
一种吡啶基桥联双四唑廉价金属配合物，其结构式如下式所示：
结构式中的R为烷基CnH2n+1、芳基、吡啶基、呋喃基或噻吩基，Y为氢或氯；其中n为0-10(优选1-6)的整数，芳基为取代或未取代的芳基，取代芳基的取代基团为甲基、甲氧基、卤素、三氟甲基中的至少一种，取代基的个数为1-5；M为Fe、Co、Ni或Mn；X为氯、溴或碘。
一种上述吡啶基桥联双四唑廉价金属配合物的合成方法，利用吡啶基桥联双四唑化合物2与廉价金属卤化物3在有机溶剂中发生配位反应，形成具有较高催化活性的金属配合物。反应结束后按常规分离纯化方法进行分离和表征，得到金属配合物1。
吡啶基桥联双四唑化合物2为合成子，其结构式如下：
结构式中的R为烷基CnH2n+1、芳基，Y为氢或氯；其中n为0-10(优选1-6)的整数，芳基为取代或未取代的芳基，取代芳基的取代基团为甲基、甲氧基、卤素、三氟甲基中的至少一种，取代基个数为1-5。
廉价金属卤化物3为MX2，其中M为Fe、Co、Ni或Mn，X为氯、溴或碘。
金属配合物1的合成路线如下述反应式所示：
进一步地，在上述技术方案中，吡啶基桥联双四唑化合物2与廉价金属卤化物3的反应溶剂为二氯甲烷、四氢呋喃、甲醇、乙醇、甲苯中的一种或者两种以上。
进一步地，在上述技术方案中，吡啶基桥联双四唑化合物2与金属卤化物3的摩尔比为1:1-1.1:1。
进一步地，在上述技术方案中，吡啶基桥联双四唑化合物2与金属卤化物3的反应温度为20-110℃。
进一步地，在上述技术方案中，吡啶基桥联双四唑化合物2与金属卤化物3的反应时间为1-24h。
制备得到的吡啶基桥联双四唑廉价金属配合物1可用于催化酮的转移氢化或酮的α-烷基化反应。所述酮类化合物其结构如下所示：
结构式中的R1为碳原子数为1-4的烷基、芳基、萘基、吡啶基、呋喃基或噻吩基；R2为氢、碳原子数为1-5的烷基或芳基。
本发明利用吡啶基桥联双四唑化合物与廉价金属卤化物配位，合成具有较高催化活性的金属配合物，制备方法简单、产率高(可高达90％以上)。本发明具有操作简便、反应条件温和、合成效率高等优点。
本发明具有以下优点：
1)金属配合物合成路线简单，条件温和，可以方便快捷的合成出目标产物。
2)制备得到的金属配合物性质稳定，对空气不敏感，易于保存。配合物催化剂在空气中放置半年，仍具有很高的催化活性。
3)制备得到的金属配合物在酮的转移氢化、酮的α-烷基化反应中具有很好的催化活性。
具体实施方式
本发明以吡啶基桥联双四唑化合物2为原料，与廉价金属卤化物3在有机溶剂中发生配位反应，合成金属配合物1，配合物1可用于催化酮的转移氢化反应或酮的α-烷基化反应。
通过下述实施例有助于进一步理解本发明，但本发明的内容并不仅限于此。
下述实施例中的原料吡啶基桥联双四唑化合物2(Synthesis 1989,9,715-718；Radiochim.Acta.2009,97,593-601；Chin.J.Catal.2018,39,327-333)按文献方法制备。
实施例1
氮气条件下，吡啶基桥联双四唑化合物2a(198mg,0.5mmol)、氯化亚铁3a(63mg,0.5mmol)在10mL的四氢呋喃中室温搅拌反应6h。减压下除去挥发组份，得到黄色固体为目标产物1aa(211mg，收率81％)。目标产物通过高分辨质谱与元素分析测定得到确认。HRMScalcd.for C21H17Cl2FeN9:521.0333；Found:521.0321。Anal.Calcd for C21H17Cl2FeN9:C,48.30；H,3.28；N,24.14.Found:C,48.39；H,3.24；N,24.09。
实施例2
反应步骤与操作同实施例1，与实施例1不同之处在于，体系反应时间为18h。停止反应后，经后处理得到黄色固体为目标产物1aa(230mg，收率88％)。说明延长反应时间可以增加目标产物收率。
实施例3
反应步骤与操作同实施例1，与实施例1不同之处在于，反应溶剂为甲苯，反应温度为80℃。停止反应后，经后处理得到黄色固体为目标产物1aa(185mg，收率71％)。说明在非质子性溶剂中也能进行此反应。
实施例4
反应步骤与操作同实施例1，与实施例1不同之处在于，反应溶剂为二氯甲烷/乙醇(v/v，1/1)，反应温度为30℃。停止反应后，经后处理得到黄色固体为目标产物1aa(214mg,收率82％)。说明在混合溶剂中也能进行此反应。
实施例5
反应步骤与操作同实施例1，与实施例1不同之处在于，体系反应温度为65℃。停止反应后，经后处理得到黄色固体为目标产物1aa(227mg,收率87％)。
实施例6
反应步骤与操作同实施例1，与实施例1不同之处在于，反应体系中加入的是吡啶基桥联双四唑化合物2b(181mg,0.5mmol)，二溴化镍3b(109mg,0.5mmol)。停止反应后，经后处理得到黄色固体为目标产物1bb(261mg,收率90％)。目标产物通过高分辨质谱与元素分析测定得到确认。HRMS calcd.for C15H20Br2ClN9Ni:576.9250；Found:576.9241。Anal.Calcd for C15H20Br2ClN9Ni:C,31.04；H,3.47；N,21.72.Found:C,31.07；H,3.46；N,21.69。
实施例7
反应步骤与操作同实施例2，与实施例2不同之处在于，反应体系中加入的是吡啶基桥联双四唑化合物2c(235mg,0.55mmol)，二氯化锰3c(63mg,0.5mmol)。停止反应后，经后处理得到黄色固体为目标产物1cc(271mg,收率91％)。目标产物通过高分辨质谱与元素分析测定得到确认。HRMS calcd.for C19H10Cl5MnN9:593.8882；Found:593.8876。Anal.Calcdfor C19H10Cl5MnN9:C,38.25；H,1.69；N,21.13.Found:C,38.21；H,3.71；N,21.15。
应用例1
在氮气保护下，一25mL封管中加入配合物1aa(10.0μmol)、叔丁醇钾(0.2mmol)、苯乙酮4a(0.2mmol)、苯甲醇5a(0.3mmol)和1.0mL甲苯，混合物在油浴140℃封管搅拌反应48小时。反应结束后，硅胶柱层析(淋洗液：石油醚(60-90℃)/二氯甲烷，v/v＝2:1)，得到白色固体产品1,3-二苯基-1-丙酮6aa(35mg，收率84％)。说明本发明的配合物可作为酮的α-烷基化反应催化剂使用。
应用例2
在氮气保护下，将底物苯乙酮4a(2.0mmol)、配合物1bb(0.1mmol)和16.0mL异丙醇5b的混合物在82℃搅拌反应5分钟。然后将4.0mL iPrOK的异丙醇溶液(0.1M)加入反应体系中。在指定的时间内，抽取0.1mL的反应液，并立即用0.5mL冷异丙醇稀释淬灭后做气相色谱分析。反应8小时，苯乙酮4a以92％的转化率还原为对应的醇产物7ab，说明本发明的配合物可作为潜在的酮还原催化剂使用。
应用例3
反应步骤与操作同应用例1，与应用例1不同之处在于配合物1aa在干燥器中放置半年。停止反应后，得到白色固体产品1,3-二苯基-1-丙酮6aa(34mg，收率81％)。说明该配合物催化剂性质稳定。
Claims (16)
1.一种吡啶基桥联双四唑廉价金属配合物，其结构式如下式所示：
结构式中的R为烷基CnH2n+1、吡啶基、呋喃基或噻吩基，Y为氢或氯；其中n为0-10的整数；
M为Fe、Co、Ni或Mn；
X为氯、溴或碘。
2.一种权利要求1所述的吡啶基桥联双四唑廉价金属配合物的合成方法，其特征在于：利用吡啶基桥联双四唑化合物2与廉价金属卤化物3进行反应合成金属配合物1；
吡啶基桥联双四唑化合物2的结构式如下：
结构式中的R为烷基CnH2n+1、吡啶基、呋喃基或噻吩基；其中n为0-10的整数；Y为氢或氯；
廉价金属卤化物3为MX2，其中M为Fe、Co、Ni或Mn，X为氯、溴或碘；
金属配合物1的合成路线如下述反应式所示：
3.如权利要求2所述的合成方法，其特征在于：吡啶基桥联双四唑化合物2与廉价金属卤化物3的反应溶剂为二氯甲烷、四氢呋喃、甲醇、乙醇、甲苯中的一种或者两种以上。
4.如权利要求2所述的合成方法，其特征在于：吡啶基桥联双四唑化合物2与廉价金属卤化物3的摩尔比为1:1-1.1:1。
5.如权利要求2所述的合成方法，其特征在于：吡啶基桥联双四唑化合物2与廉价金属卤化物3的反应温度为20-110℃。
6.如权利要求2所述的合成方法，其特征在于：吡啶基桥联双四唑化合物2与廉价金属卤化物3的反应时间为1-24h。
7.一种权利要求1所述的吡啶基桥联双四唑廉价金属配合物用于催化酮的转移氢化或酮的α-烷基化反应中的应用。
8.如权利要求7所述的应用，其特征在于：所述酮的结构式如下式所示：
结构式中的R1为碳原子数为1-4的烷基、萘基、吡啶基、呋喃基或噻吩基；R2为氢、碳原子数为1-5的烷基、或芳基。
9.一种吡啶基桥联双四唑廉价金属配合物，其结构式如下式1aa、1bb或1cc所示：
10.一种权利要求9所述的吡啶基桥联双四唑廉价金属配合物的合成方法，其特征在于：利用吡啶基桥联双四唑化合物2与廉价金属卤化物3进行反应合成金属配合物1，金属配合物1为1aa、1bb或1cc；
吡啶基桥联双四唑化合物2的结构式如下2a、2b或2c：
廉价金属卤化物3为氯化亚铁3a、二溴化镍3b或二氯化锰3c；
金属配合物1的合成路线如下述反应式所示：
11.如权利要求10所述的合成方法，其特征在于：吡啶基桥联双四唑化合物2与廉价金属卤化物3的反应溶剂为二氯甲烷、四氢呋喃、甲醇、乙醇、甲苯中的一种或者两种以上。
12.如权利要求10所述的合成方法，其特征在于：吡啶基桥联双四唑化合物2与廉价金属卤化物3的摩尔比为1:1-1.1:1。
13.如权利要求10所述的合成方法，其特征在于：吡啶基桥联双四唑化合物2与廉价金属卤化物3的反应温度为20-110℃。
14.如权利要求10所述的合成方法，其特征在于：吡啶基桥联双四唑化合物2与廉价金属卤化物3的反应时间为1-24h。
15.一种权利要求9所述的吡啶基桥联双四唑廉价金属配合物用于催化酮的转移氢化或酮的α-烷基化反应中的应用。
16.如权利要求15所述的应用，其特征在于：所述酮的结构式如下式所示：
结构式中的R1为碳原子数为1-4的烷基、萘基、吡啶基、呋喃基或噻吩基；R2为氢、碳原子数为1-5的烷基、或芳基。
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