CN105732667B - 四核铜配合物及制备方法和催化四氢呋喃气相胺化的应用 - Google Patents
四核铜配合物及制备方法和催化四氢呋喃气相胺化的应用 Download PDFInfo
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 title claims abstract description 77
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 31
- 238000005576 amination reaction Methods 0.000 title claims abstract description 26
- 150000001879 copper Chemical class 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 27
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- JEYWNNAZDLFBFF-UHFFFAOYSA-N Nafoxidine Chemical compound C1CC2=CC(OC)=CC=C2C(C=2C=CC(OCCN3CCCC3)=CC=2)=C1C1=CC=CC=C1 JEYWNNAZDLFBFF-UHFFFAOYSA-N 0.000 claims abstract description 15
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
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- -1 perchlorate anion Chemical class 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
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- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 3
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- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
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- RCIMBBZXSXFZBV-UHFFFAOYSA-N piromidic acid Chemical compound N1=C2N(CC)C=C(C(O)=O)C(=O)C2=CN=C1N1CCCC1 RCIMBBZXSXFZBV-UHFFFAOYSA-N 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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
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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
- 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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- 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
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
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- 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
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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Abstract
本发明公开了四核铜配合物及制备方法和催化四氢呋喃气相胺化的应用，涉及四氢吡咯催化剂领域。四核铜配合物化学式为[Cu(L)(ClO4)(H2O)](dioxane)1.5，式中L为2,3,5,6‑四氯‑1,4‑双(咪唑‑1‑羰基)苯配体，ClO4为硝酸根阴离子，dioxane为1,4‑二氧六环。采用六水合高氯酸铜与有机配体2,3,5,6‑四氯‑1,4‑双(咪唑‑1‑羰基)苯在1,4‑二氧六环和甲醇的溶合溶剂中，在封闭条件下经由热反应得到具有四核笼状结构的铜配合物。应用于四氢呋喃和氨气氨化制得四氢吡咯。本发明工艺流程简单；催化剂制备方便，重现性好；四氢呋喃转化率达83%，四氢吡咯的选择性达95%。
Description
技术领域
本发明涉及四氢吡咯催化剂领域，具体涉及一种四核铜配合物及其制备方法和催化四氢呋喃气相胺化的应用。
背景技术
四氢吡咯，又称吡咯烷，英文名为Tetrahydropyrrole或Pyrrolidine，分子式C4H9N，沸点87℃，密度0.852g cm–3，作为一个环状的二级胺，pKb＝2.9，具有一般胺性质，在多方面有着极其广泛的用途。在药物合成领域，结构中直接有四氢吡咯结构的药物就要许多种，如治脑血管障碍性疾病的丁咯地尔，具有镇痛功能的酒石酸右吗拉胺，抗震颤麻痹药普环定，抗感染药吡咯米酸，局部麻药吡咯卡因，搞抑郁药丙苯乙吡咯等等。此外，四氢吡咯在农药、日用化学品、涂料、纺织、高分子材料等领域也有着广泛的用途。
合成四氢吡咯主要可采用环化反应和环转化反应两类。环化反应中根据起始原料的不同，文献报道了以下几类制备方法，分别为丁二醇和氨气为原料的气相催化法(Murahashi S.,Kondo K.,Hakata T.J.Tetrahedron Letters 1982,23,229–232)、氨醇为原料的气相催化法(Hammerschmidt W.,Baiker A.,Wokaun A.,Fluhr W.AppliedCatalysis 1986,20,305–312)、1,4-丁二胺为原料的气相催化法(Yasurnura J.NipponKagaku Zasshi 1961,82,1700–1702)以及丁二腈为原料的环化催化加氢法(Serra M.,Salagre P.,Cesteros Y.Medina F.,Sueiras J.E.Journal of Catalysis 2001,197,210–219)等。环转化法，主要是采用吡咯为原料催化加氢(Moravek V.Applied Catalysis1990,66,257–266)或者采用四氢呋喃为原料与氨气气相催化(Fujita K.,Hatada K.,OnoY.,Keii T.Journal of Catalysis 1974,35,325–329)合成四氢吡咯。环化反应催化剂昂贵，部分方法中合成路线长，副产物多，收率低，不具备实际工业操作的价值。以四氢呋喃和氨气为原料，通过气相催化法制备四氢吡咯，具有原料成本低，这条合成路线在生产中使用，但仍然存在一些问题，如使用的催化剂转化率低，选择性不高。
因此，设计开发催化四氢呋喃气相胺化新的高效催化剂，以提高相反应的转化率和选择性已成当前合成四氢吡咯的一大热点，也为开发研究各种含有四氢吡咯靶向结构的药物开发和生产注入强大的生命力。
发明内容
本发明的目的是为了进一步拓展金属配合物应用于催化四氢呋喃气相胺化制备四氢吡咯，公开一种四核铜配合物及其制备方法和催化四氢呋喃气相胺化的应用。该铜配合物制备方便，重现性好；对四氢呋喃气相胺化具有较好的催化活性，四氢呋喃转化率达83％，四氢吡咯的选择性达95％。
本发明一种应用于催化四氢呋喃气相胺化的四核铜配合物，其化学式为[Cu(L)(ClO4)2(H2O)](dioxane)1.5，式中ClO4为硝酸根阴离子，dioxane为1,4-二氧六环，L为2,3,5,6-四氯-1,4-双(咪唑-1-羰基)苯配体。
本发明一种四核铜配合物，其二级结构单元为：晶体属于正交晶系，空间群为Cmca，分子式为C20H20Cl6CuN4O14，分子量为816.66；晶胞参数为： α＝β＝γ＝90°，晶胞体积为基本结构是一个零维四核的结构。
所述的一种四核铜配合物的制备方法，按照下述步骤进行：将2,3,5,6-四氯-1,4-双(咪唑-1-羰基)苯、六水合高氯酸铜和(1,4-二氧六环与甲醇)的混合溶剂放入反应器中，封闭后，于120℃反应24小时；反应结束后降温到室温，得到的晶体，再用乙醇洗涤，经干燥制得一种四核铜的配合物。
上述技术方案中，按摩尔比，2,3,5,6-四氯-1,4-双(咪唑-1-羰基)苯:六水合高氯酸铜＝1:1。
上述技术方案中，1,4-二氧六环和甲醇的体积比为1:1。
上述技术方案中，每1毫摩尔的2,3,5,6-四氯-1,4-双(咪唑-1-羰基)苯对应70mL的1,4-二氧六环。
上述技术方案中，降温速率为5℃/小时。
所述的一种四核铜配合物催化四氢呋喃气相胺化的应用方法，其特征在于按照下述步骤进行：将权利1所述一种四核铜配合物装入管式固定床反应器中间段中,在反应温度220℃下，通入计量的四氢呋喃和氨气，经催化剂层气相氨化制得四氢吡咯。
本发明所述催化四氢呋喃气相胺化过程中，四核铜配合物的接触时间达25.2g h–1/mol，四氢呋喃和氨气的摩尔比为1:3。
本发明的优点：本发明工艺流程简单；催化剂制备方便，重现性好；四氢呋喃转化率达83％，四氢吡咯的选择性达95％。
附图说明
其中图1为铜配合物的配位环境图(左)及笼状结构示意图(右)；
其中图2为铜配合物的的热重示意图；
其中图3为铜配合物催化四氢呋喃气相胺化工艺流程示意图(1:氨气钢瓶；2:转子流量计；3:固定床反应器；4:反应器测温控温装置；5:冷凝器；6:接收瓶；7:计量泵；8:原料瓶；9:尾气吸收装置)。
具体实施方式
实验例1铜配合物的制备：
(I)四氯对苯二甲酰氯的合成
称取10.0g(0.033mol)四氯对苯二甲酸加入250mL四口烧瓶中，再分别量取3mL(0.038mol)精制DMF和90mL(1.23mol)氯化亚砜先后倒入四口烧瓶中，搅拌，升温至78℃，并保持此温度回流反应4h，结束反应。先常压再减压蒸馏出过量的氯化亚砜后用少量石油醚冲洗，再用适量无水乙醇洗涤，干燥后得白色固体四氯对苯二甲酰氯10.4g，收率92.7％，m.p.142～143℃。
(II)2,3,5,6-四氯-1,4-双(咪唑-1-羰基)苯的合成
量取120mL四氢呋喃溶解10.42g(0.03)的四氯对苯二甲酰氯于250mL四口烧瓶中，并称取4.18g(0.06mol)咪唑于四口烧瓶中，然后再称取6.20g(0.06mol)缚酸剂三乙胺于滴液漏斗中，冰浴至0-5℃时开始滴加三乙胺，约1小时滴加完三乙胺后常温搅拌24小时，常压蒸馏出四氢呋喃后分别用水和饱和NaCO3溶液洗涤，干燥后得淡黄色固体21.4g，收率88.4％。1H-NMR(DMSO,ppm)：δ：7.735(s,1H,CH)；8.091(d,1H,CH,J＝8Hz)；8.549(t,1H,CH)。IR(KBr,cm–1)：3430b,3126w,1723vs,1686w,1535w,1473w,1413w,1303m,1250s,913w,637w。
(III)铜配合物的合成
370mg六水合高氯酸铜(1毫摩尔)、400mg 2,3,5,6-四氯-1,4-双(咪唑-1-羰基)苯(1毫摩尔)，70mL甲醇和70mL二氧六环的混合物，在室温下搅拌15分钟，然后转移到200mL内衬四氟乙烯的不锈钢高压釜中，升温至120℃保温24小时，然后以每小时5℃速率，降至室温，得到绿色块状晶体，晶体用50mL甲醇洗涤，自然干燥，制得一种铜配合物，产率为62％。
主要的红外吸收峰为(KBr/cm–1)：3429b，3139w，1750vs，1683w，1489w，1406w，1367m，1340w，1283w，1239m，1114s，629w。
试验一铜配合物的表征
(1)铜配合物的结构测定
晶体结构测定采用布Apex II CCD衍射仪，于293(2)K下，用经石墨单色化的Mo Kα射线以ω扫描方式收集衍射点，收集的数据通过SAINT程序还原并用SADABS方法进行半经验吸收校正。结构解析和精修分别采用SHELXTL程序的SHELXS和SHELXL完成，通过全矩阵最小二乘方法对F2进行修正得到全部非氢原子的坐标及各向异性参数。所有氢原子在结构精修过程中被理论固定在母原子上，赋予比母原子位移参数稍大(C–H，1.2或O–H，1.5倍)的各向同性位移参数。详细的晶体测定数据见表1。结构见图1–2。图1：铜配合物的配位环境图。
(2)配合物的热稳定性表征
配合物的热稳定性可通过热重分析仪来表征，结果表明，该铜配合物具有高的热稳定性，能稳定到300℃。见图2：铜配合物的热重示意图。(仪器型号：NETZSCH/TG 209F3)。
试验二配合物的预处理
将5g铜配合物在200℃真空干燥12小时，然后在氮气保护下，缓慢冷却备用。
试验三催化四氢呋喃气相胺化工艺流程
实验方案中，采用自行设计的固定床反应器，固定床反应以Φ8mm×350mm不锈钢管制成，将3g处理好的铜配合物填入床层中间段恒温区，床层两端填以瓷环填料。反应管由熔盐加热，两支热电偶分别插入催化剂床层和熔盐介质测定二者温度并与控温设备相连。见图3：铜配合物催化四氢呋喃气相胺化工艺流程示意图。
试验四评价铜配合物催化四氢呋喃气相胺化制备四氢吡咯
四氢呋喃由计量泵输入，在反应管上端填料层气化；氨气自钢瓶经由转子流量计后进入固定床反应器上部，与四氢呋喃在上部填料层充分混合后，进入反应器催化剂层，在220℃下进行反应，四氢呋喃和氨气的摩尔比为1:3，铜配合物的接触时间达15.2g h–1/mol。反应得到的混合产物经由固定床反应器的下端填料层，至冷凝器充分冷凝后，尾气通入吸收槽后放空。连续反应24小时后，采用气相外标法测定粗品中四氢呋喃的转化率达85％，四氢吡咯的选择性达92％。
表1 铜配合物的主要晶体学数据
。
Claims (9)
1.一种应用于催化四氢呋喃气相胺化的四核铜配合物，其特征在于其化学式为[Cu(L)(ClO4)2(H2O)](dioxane)1.5，式中ClO4为高氯酸根阴离子，dioxane为1,4-二氧六环，L为2,3,5,6-四氯-1,4-双(咪唑-1-羰基)苯配体。
2.根据权利要求1所述的一种应用于催化四氢呋喃气相胺化的四核铜配合物，其特征在于其二级结构单元为：晶体属于正交晶系，空间群为Cmca，分子式为C20H20Cl6CuN4O14，分子量为816.66；晶胞参数为：a = 29.821(3) Å, b = 26.061(3) Å，c = 16.631(2) Å，α = β = γ = 90°，晶胞体积为12925(2) Å3。
3.根据权利要求1或2所述的一种应用于催化四氢呋喃气相胺化的四核铜配合物的制备方法，其特征在于按照下述步骤进行：将2,3,5,6-四氯-1,4-双(咪唑-1-羰基)苯、六水合高氯酸铜和（1,4-二氧六环与甲醇）的混合溶剂放入反应器中，封闭后，于120℃反应24小时；反应结束后降温到室温，得到的晶体，再用乙醇洗涤，经干燥制得一种四核铜的配合物。
4.根据权利要求3所述的一种应用于催化四氢呋喃气相胺化的四核铜配合物的制备方法，其特征在于按摩尔比，2,3,5,6-四氯-1,4-双(咪唑-1-羰基)苯 : 六水合高氯酸铜 = 1: 1。
5.根据权利要求3所述的一种应用于催化四氢呋喃气相胺化的四核铜配合物的制备方法，其特征在于1,4-二氧六环和甲醇的体积比为1 : 1。
6.根据权利要求3所述的一种应用于催化四氢呋喃气相胺化的四核铜配合物的制备方法，其特征在于：每1毫摩尔的2,3,5,6-四氯-1,4-双(咪唑-1-羰基)苯对应70 mL的1,4-二氧六环。
7.根据权利要求3所述的一种应用于催化四氢呋喃气相胺化的四核铜配合物的制备方法，其特征在于：降温速率为5℃/小时。
8.根据权利要求1或2所述的一种应用于催化四氢呋喃气相胺化的四核铜配合物催化四氢呋喃气相胺化的应用方法，其特征在于按照下述步骤进行：将权利要求1或2所述一种四核铜配合物装入管式固定床反应器中间段中, 在反应温度220℃下，通入计量的四氢呋喃和氨气，经催化剂层气相氨化制得四氢吡咯。
9.根据权利要求8所述的一种应用于催化四氢呋喃气相胺化的四核铜配合物催化四氢呋喃气相胺化的应用方法，其特征在于四核铜配合物的接触时间达25.2 g h–1/mol，四氢呋喃和氨气的摩尔比为1 : 3。
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