CN110305167A - 一种手性铂配合物的制备及用途 - Google Patents

一种手性铂配合物的制备及用途 Download PDF

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CN110305167A
CN110305167A CN201910526005.0A CN201910526005A CN110305167A CN 110305167 A CN110305167 A CN 110305167A CN 201910526005 A CN201910526005 A CN 201910526005A CN 110305167 A CN110305167 A CN 110305167A
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platinum complex
coordination compound
reaction
chiral
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罗梅
彼得·史唐
李国雄
谢蓝
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Hefei University of Technology
Hefei Polytechnic University
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Hefei Polytechnic University
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P35/00—Antineoplastic agents
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/16—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of hydrazones
    • 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 System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0086—Platinum compounds
    • C07F15/0093—Platinum 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
    • 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
    • B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
    • 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
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/828—Platinum

Abstract

一种手性铂配合物，其化学式如下：该手性配合物(I)的合成方法是称取Pt(DMSO)2(NO3)2 0.0366g，用30mL氯苯做溶剂溶解，再加入1,4‑(4R)‑二苯基－2－噁唑啉基苯0.0337g，回流反应48小时后停止反应，将滤液旋干，再加入二氯甲烷及DMF溶剂，自然挥发得一种新铂配合物单晶。该手性配合物(I)的用途，是作为催化剂在二苯甲酮腙的缩合反应应用，其转化率达99％。该手性配合物(I)在多种癌细胞如：A549(肺癌)、KB(鼻咽癌)和KB‑VIn(抗耐药性鼻咽癌)试验中均显示出较强的抑制活性。

Description

一种手性铂配合物的制备及用途
一、技术领域
本发明涉及一种金属有机配位化合物(配合物)及其制备方法，特别涉及含硫金属有机配合物及其制备方法，确切地说是一种铂配合物晶体及其合成方法。
二、背景技术
金属铂配合物因其在抗癌和分子磁体、荧光材料等方面的潜在应用价值已引起人们的广泛关注。金属铂配合物的合成方法近年来有许多文献报道。【1-2】
1.Cis/trans influences in platinum(II)complexes.X-ray crystalstructures of cis-dichloro(dimethyl sulfide)(dimethyl sulfoxide)platinum(II)and cis-dichloro(dimethyl sulfide)(dimethyl phenyl phosphine)platinum(II)，Journal of Molecular Structure，470，1-2，39-47.
2.Design of chiral macrocyclic complexes based on trans-chelation ofn:n metal-bidentate P,N-or N,N-ligands，Chemistry Letters(2006),35,(2),172-173。
三、发明内容
本发明旨在提供一种Pt-N金属有机配合物以应用于催化领域，所要解决的技术问题遴选作为配体并合成锌配合物。
本发明所称的铂配合物一种是由二甲亚砜硝酸铂与1,4-(4R)-二苄基－2－噁唑啉基苯制备的由以下化学式所示的配合物：
化学名称：[1,4-(4R)-二苄基－2－噁唑啉基苯]硝酸铂配合物，简称配合物(I)。
该本手性配合物(I)的合成方法包括反应、分离和纯化，所述的合成是称取Pt(DMSO)2(NO3)2 0.0366g用30mL氯苯做溶剂溶解，再加入1,4-(4R)-二苯基－2－噁唑啉基苯0.0337g，回流反应48小时后停止反应，将滤液旋干，再加入二氯甲烷及DMF溶剂，自然挥发得一种新铂配合物单晶。
合成反应如下：
该配合物在二苯甲酮腙的缩合反应中显示一定的的催化性能，其转化率达57％。
该配合物在A549(肺癌)、KB(鼻咽癌)和KB-VIn(抗耐药性鼻咽癌)试验中均显示出较强的抑制活性。
本合成方法一步得到目标产物，工艺简单，操作方便。
四、附图说明
图1铂配合物晶体的X-衍射分析图。
五、具体实施方式
1.二氯化铂二甲亚砜配合物
在100mL两口瓶中,加入二氯化铂1.2042g,10mLDMSO，二氯甲烷30mL,将混合物回流60h,停止反应,静止，得二甲亚砜铂配合物固体,产率45％；元素分析：测试值：C:11.78％,H:2.91％；计算值：C:11.38％,H 2.86％；IR(KBr):1157,1134，450,430。
2.二甲亚砜二硝酸铂配合物
在两口瓶中加入0.3521g二甲亚砜氯化铂,0.5135g硝酸银，用20mL二氯甲烷做溶剂，铝箔纸避光室温做反应30小时，过滤，用二氯甲烷/三氯甲烷体积比为1/1配制溶液，自然挥发得二甲亚砜硝酸铂配合物固体备用；产率42％。
3.铂配合物晶体的制备
称取Pt(DMSO)2(NO3)2 0.0366g用30mL氯苯做溶剂溶解，再加入1,4-(4R)-二苯基－2－噁唑啉基苯0.0337g，回流反应48小时后停止反应，将滤液旋干，再加入二氯甲烷及DMF溶剂，自然挥发得一种新铂配合物单晶；产率68％,熔点：212-214℃；[a]5 D＝-40.8°(c0.0104,DMF),元素分析：测试值：C:47.69％,H:3.92％,N:6.56％；计算值：C:47.78％,H3.70％,N:6.43％；IR(KBr):3254,3057,1632,1494,1454,1431,1384,1329,1302,1180,1161,1078,1033,997,934,920；配合物晶体数据如下：
晶体典型的键长数据：
11-X,1/2+Y,3/2-Z；21-X,-1/2+Y,3/2-Z
晶体典型的键角数据：
11-X,1/2+Y,3/2-Z；21-X,-1/2+Y,3/2-Z
4.二苯甲酮腙的缩合反应应用
称取0.0234g二苯甲酮腙和脲素0.027g放置于25mL小烧瓶中，加入2mLTHF及化合物I 0.0234g，常温下搅拌48h，取少量样品做核磁检测，转化率>99％；1H NMR(600MHz,CDCl3,27℃),δ7.50–7.44(m,4H),7.43–7.36(m,6H),7.36–7.25(m,10H)；13C NMR(100MHz,CDCl3)δ158.93,138.20,135.56,129.60,129.34,128.68,128.66,128.04,127.88.；IR:3422,3057,1664,1622,1491,1444,1321,1278,1176,1076,1028,956,914,767,694,655。
5.抗癌活性应用
本发明依据活性天然产物的结构设计合成的铂配合物在多种癌细胞如：
A549(肺癌)、KB(鼻咽癌)和KB-VIn(抗耐药性鼻咽癌)试验中均显示出较强的抑制活性(ED50＜10.0μg/mL)。因此，预期本发明的化合物可用于治疗多种癌症，例如肺癌、乳腺癌、口腔癌细胞、乳腺癌细胞。本发明化合物的部分抗癌活性测试结果见表1。
表1.铂配合物(I)的抗癌活性数据

Claims (5)

1.一种手性铂配合物，其化学式如下：
2.由权利要求1所述的一种手性铂配合物(I)，在99.99(10)K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单斜晶系,C2；其晶胞参数：α＝90°；β＝90°；γ＝90°。
3.由权利要求1所述的手性配合物(I)的合成方法包括反应、分离和纯化，所述的合成用30mL氯苯做溶剂溶解，再加入1,4-(4R)-二苯基－2－噁唑啉基苯0.0337g，回流反应48小时后停止反应，将滤液旋干，再加入二氯甲烷及DMF溶剂，自然挥发得一种新铂配合物单晶。
4.由权利要求1所述的所述的的一种手性配合物(I)的用途，是作为催化剂在二苯甲酮腙的缩合反应应用，其转化率达99％。
5.由权利要求1所述的所述的的一种手性配合物(I)的用途,其可用作抗癌试剂在A549(肺癌)、KB(鼻咽癌)和KB-VIn(抗耐药性鼻咽癌)试验中均显示出较强的抑制活性。
CN201910526005.0A 2019-06-18 2019-06-18 一种手性铂配合物的制备及用途 Pending CN110305167A (zh)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110746466A (zh) * 2019-10-22 2020-02-04 合肥工业大学 一种手性铂配合物的制备及用途
CN111718362A (zh) * 2020-07-29 2020-09-29 合肥工业大学 一种手性锌配合物制备及用途
CN114656417A (zh) * 2022-04-08 2022-06-24 合肥工业大学智能制造技术研究院 一种手性噁唑啉的合成方法及用途

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CN105001268A (zh) * 2015-08-13 2015-10-28 合肥祥晨化工有限公司 一种手性噁唑啉铂配合物晶体及其合成方法
CN105198935A (zh) * 2015-10-02 2015-12-30 合肥祥晨化工有限公司 一种手性噁唑啉钯配合物
CN106800576A (zh) * 2017-01-19 2017-06-06 合肥祥晨化工有限公司 一种手性铂配合物晶体的制备及合成方法

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Publication number Priority date Publication date Assignee Title
CN105001268A (zh) * 2015-08-13 2015-10-28 合肥祥晨化工有限公司 一种手性噁唑啉铂配合物晶体及其合成方法
CN105198935A (zh) * 2015-10-02 2015-12-30 合肥祥晨化工有限公司 一种手性噁唑啉钯配合物
CN106800576A (zh) * 2017-01-19 2017-06-06 合肥祥晨化工有限公司 一种手性铂配合物晶体的制备及合成方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110746466A (zh) * 2019-10-22 2020-02-04 合肥工业大学 一种手性铂配合物的制备及用途
CN110746466B (zh) * 2019-10-22 2023-08-15 合肥工业大学 一种手性铂配合物的制备及用途
CN111718362A (zh) * 2020-07-29 2020-09-29 合肥工业大学 一种手性锌配合物制备及用途
CN111718362B (zh) * 2020-07-29 2023-06-20 合肥工业大学 一种手性锌配合物制备及用途
CN114656417A (zh) * 2022-04-08 2022-06-24 合肥工业大学智能制造技术研究院 一种手性噁唑啉的合成方法及用途
CN114656417B (zh) * 2022-04-08 2023-10-13 合肥工业大学智能制造技术研究院 一种手性噁唑啉的合成方法及用途

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