CN113087728A - 一种铜配合物 - Google Patents
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- CN113087728A CN113087728A CN202110303423.0A CN202110303423A CN113087728A CN 113087728 A CN113087728 A CN 113087728A CN 202110303423 A CN202110303423 A CN 202110303423A CN 113087728 A CN113087728 A CN 113087728A
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- 150000004699 copper complex Chemical class 0.000 title claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims abstract description 7
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- XXRCUYVCPSWGCC-UHFFFAOYSA-N Ethyl pyruvate Chemical compound CCOC(=O)C(C)=O XXRCUYVCPSWGCC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006842 Henry reaction Methods 0.000 claims abstract description 4
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- 239000012153 distilled water Substances 0.000 claims abstract description 4
- 229940117360 ethyl pyruvate Drugs 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000010992 reflux Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims 1
- 238000002447 crystallographic data Methods 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- RHAIEOZTWMTHSS-UHFFFAOYSA-L Cl[Cu]Cl.O.O.Cl Chemical compound Cl[Cu]Cl.O.O.Cl RHAIEOZTWMTHSS-UHFFFAOYSA-L 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- CWKVFRNCODQPDB-UHFFFAOYSA-N 1-(2-aminoethylamino)propan-2-ol Chemical compound CC(O)CNCCN CWKVFRNCODQPDB-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- XUEWIQNQPBSCOR-UHFFFAOYSA-N 2-nitro-1-phenylethanol Chemical compound [O-][N+](=O)CC(O)C1=CC=CC=C1 XUEWIQNQPBSCOR-UHFFFAOYSA-N 0.000 description 1
- BISHACNKZIBDFM-UHFFFAOYSA-N 5-amino-1h-pyrimidine-2,4-dione Chemical compound NC1=CNC(=O)NC1=O BISHACNKZIBDFM-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- GJCXHYNLSNVSQZ-UHFFFAOYSA-L [Cu](Cl)Cl.Cl Chemical compound [Cu](Cl)Cl.Cl GJCXHYNLSNVSQZ-UHFFFAOYSA-L 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 238000005303 weighing Methods 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
-
- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
- B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
一种铜配合物，其化学式如下：
该铜配合物的合成方法是向烧瓶中加入25mL无水甲醇，再加入25mL蒸馏水。加入5‑氨基脲嘧啶1.0170g(0.008mol)加入上述溶液，加入磁力搅拌子，打开开关，搅拌5分钟后加入1.3692g(0.008mol)二水合氯化铜。回流加热48小时，停止加热后趁热过滤.静置待溶液挥发，得到绿色晶体。该铜配合物(I)的用途，是该配合物在丙酮酸乙酯的亨利反应中显示了一定的催化性能，其转化率分别达96.3％。
Description
一、技术领域
本发明涉及一种新化合物及其用途，特别涉及一种铜配合物及其制备方法，确切地说是一种铜配合物的制备及用途。
二、背景技术
铜配合物是重要的催化剂和医药化工产品，其作为催化剂在二乙基锌与苯甲醛对映选择性加成反应等反应中有较好的催化效果。
参考文献：
1..Synthesis and properties of isomeric tris(N-[2-hydroxyethyl]ethylenediamine)cobalt(III)andtris(N-[2-hydroxypropyl]ethylenediamine)cobalt(III)chlorides,arpeiskaya,E.I.；Kukushkin,Yu.N.；Trofimov,V.A.；Yakovlev,I.P.,Zhurnal Neorganicheskoi Khimii(1971),16(7),1960-4。
三、发明内容
本发明旨在提供含配合物，所要解决的技术问题是一步合成得到目标产物。
本发明所称的铜配合物是由5-氨基脲嘧啶与二水合氯化铜制备的由以下化学式所示的配合物：
化学名称：二水化二水合氯化铜盐酸盐配合物,简称配合物(I)。
该配合物在丙酮酸乙酯的亨利反应中显示了一定的催化性能，其转化率达96.3％。
本合成方法包括合成和分离，所述的合成是称取5-氨基脲嘧啶1.0170g(0.008mol),,并加入25mL无水甲醇，再加入25mL蒸馏水。搅拌5分钟后加入1.3692g(0.008mol)二水合氯化铜。回流加热48小时，停止加热后趁热过滤.静置待溶液挥发，得到绿色晶体。产率为63％。合成反应如下：
本合成方法是一步得到目标产物，工艺简单，操作方便。
该反应的反应机理可推测为二水合氯化铜在无水甲醇的水溶液中，5-氨基尿嘧啶与二水合氯化铜作用，首先形成盐酸盐，并进一步与二水合氯化铜作用，得到氯化铜盐酸盐及水化物。
四、附图说明
图1：：二水化二水合氯化铜盐酸盐配合物的单晶X-衍射图。
五、具体实施方式
铜配合物的制备：
向烧瓶中加入25mL无水甲醇，再加入25mL蒸馏水。加入5-氨基脲嘧啶1.0170g(0.008mol)加入上述溶液，加入磁力搅拌子，打开开关，搅拌5分钟后加入1.3692g(0.008mol)二水合氯化铜。回流加热48小时，停止加热后趁热过滤.静置待溶液挥发，得到绿色晶体。产率为63％，熔点：90-92℃。元素分析数据[Cl4CuH10O4]，理论值：H：3.61％；Cu:22.74％；实测值：H:3.72％；Cu:22.58％；ESI(M+1-Cl:Cl3CuH10O4):实测值：244.8586；理论值：243.9720；IR(cm-1)：3286，3141，3042，2818，1719，1583，1396，1057，539；
铜配合物的晶体数据：
晶体典型的键长数据：
Table 4 Bond Lengths for mo_201109A_0m.
11-X，1-Y，1-Z
晶体典型的键角数据：
Table 5 Bond Angles for mo_201109A_0m.
11-X,I-Y,1-Z。
亨利反应应用:
2-硝基-1-苯基乙醇
称取0.0416g(0.15mmol)铜配合物，置于25mL烧瓶中，依次加入0.5mL硝基甲烷和0.1ml丙酮酸乙酯，常温搅拌反应15小时后，进行1HNMR检测,其转化率为96.1％；1HNMR(600MHz，CDCl3):δ)4.86(d,J＝13.8Hz,1H),4.58(d,J＝13.8Hz,1H),4.34(m,2H),3.85(s,1H),1.46(s,3H),1.33(t,J＝7.2Hz,3H).13CNMR(150MHz，CDCl3):δ＝173.4,80.9,72.4,63.0,23.8,13.9。
Claims (4)
1.一种铜配合物，其化学式如下：
2.权利要求1所述的铜配合物，在293K温度下，在牛津X-射线单晶衍射仪上，用经石墨单色器单色化的MoKα射线,
以ω-θ扫描方式收集衍射数据，其特征在于晶体属四方晶系,P 21/c晶胞参数:
alpha＝90°；
beta＝90°；
gamma＝90°。
3.权利要求1所述的铜配合物的合成方法，包括合成和分离，所述的合成是：向烧瓶中加入25mL无水甲醇，再加入25mL蒸馏水。加入5-氨基脲嘧啶1.0170g(0.008mol)加入上述溶液，加入磁力搅拌子，打开开关，搅拌5分钟后加入1.3692g(0.008mol)二水合氯化铜。回流加热48小时，停止加热后趁热过滤.静置待溶液挥发，得到绿色晶体。
4.权利要求1所述的铜配合物(I)的用途，是该配合物在丙酮酸乙酯的亨利反应中显示了一定的催化性能，其转化率分别达96.3％。
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106833624A (zh) * | 2017-03-10 | 2017-06-13 | 宁波大学 | 一种蓝紫色荧光材料及其制备方法 |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106833624A (zh) * | 2017-03-10 | 2017-06-13 | 宁波大学 | 一种蓝紫色荧光材料及其制备方法 |
Non-Patent Citations (6)
| Title |
|---|
| UDAI P. SINGH等: "X-Ray Diffraction Studies on Metal Complexes of 5-Nitrouracil", 《CRYST. RES.TECHNOL》, vol. 30, no. 1, pages 13 * |
| 张志军: "含氮过渡金属有化配合物的合成、表征及催化应用", 《中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑)》, no. 2, pages 014 - 794 * |
| 徐佳: "过渡金属有机配合物的合成、表征及催化应用", 《中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑)》, no. 2, pages 014 - 767 * |
| 汪磊: "铜(Ⅱ)、钴(Ⅱ)金属配合物合成、表征及催化研究", 《中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑)》, no. 7, pages 014 - 311 * |
| 蒋丽: ""锌氮和铜氮配合物的合成、表征及催化应用", 《中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑)》, no. 4, pages 014 - 142 * |
| 邱晶晶: "Cu(Ⅱ)、Co(Ⅱ) 金属配合物合成、表征及催化活性研究", 《中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑)》, no. 1, pages 014 - 165 * |
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