CN106083616B - 一种钴配合物的制备及合成方法 - Google Patents

一种钴配合物的制备及合成方法 Download PDF

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CN106083616B
CN106083616B CN201610409957.0A CN201610409957A CN106083616B CN 106083616 B CN106083616 B CN 106083616B CN 201610409957 A CN201610409957 A CN 201610409957A CN 106083616 B CN106083616 B CN 106083616B
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cobalt complex
synthetic method
chiral
cobalt
complex
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CN106083616A (zh
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罗梅
徐磊
张鑫
齐磊
张竞成
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Hefei University of Technology
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Hefei University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C215/22—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being unsaturated
    • C07C215/28—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being unsaturated and containing six-membered aromatic rings
    • 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
    • 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
    • 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
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

一种手性(D)‑苯甘氨醇钴配合物(I)，其化学式如下：该手性苯甘氨醇钴配合物(I)的合成方法：称取4.1154g(0.03mol)D‑苯甘氨醇放入100mL圆底烧瓶中，加入50mL无水甲醇，搅拌使其溶解；将2.3794g(0.01mol)的CoCl2·6H2O加入上述溶液，加热回流48h；趁热过滤反应溶液，静置于烧杯中自然挥发，得到紫红色晶体；该配合物在苯甲醛的亨利反应显示了一定的催化性能，其转化率达79.3％。

Description

一种钴配合物的制备及合成方法
技术领域
本发明涉及一种新化合物及其制备方法，特别涉及一种钴化合物及其制备方法，确切地说是一种手性D-苯甘氨醇钴配合物的制备及合成方法。
背景技术
手性氨基醇钴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。【1-5】
参考文献：
1.Asymmetric hydrogenation catalyzed by bis(dimethylglyoximato)cobalt(II)-achiral base complex and chiral amino alcohol conjugatedsystems.Oxidoreductase model with enantioselectivity，Ohgo,Yoshiaki；Natori,Yukikazu；Takeuchi,Seiji；Yoshimura,Juji,Chemistry Letters(1974),(11),1327-30.
Synthesis,structure and acid-base properties of cobalt(III)complexeswith aminoalcohols tepanenko,O.N.；Reiter,
2.L.G.Ukrainskii Khimicheskii Zhurnal(Russian Edition),(1992),58(12),1047-54.
3.Cobalt(III)mono-and trinuclear complexes with O,N-chelatingaminoalcohols apanadze,T.Sh.；Gulya,A.P.；Novotortsev,V.M.；Ellert,O.G.；Shcherbakov,V.M.；Kokunov,Yu.V.；Bushaev,Yu.A.Koordinatsionnaya Khimiya(1991),17(7),934-40.
4.Magnetic properties of cobalt complexes with amino alcohols,Evreev,V.N.；Bogdanov,A.P.13 Vses.Chugaev.Soveshch.po Khimii Kompleks.Soedin.,1978(1978),137.
5.Synthesis,stereochemistry,and reactions of cobalt(III)complexeswith amino alcohol ligands
Okamoto,Martha S.No Corporate Source data available|(1974),146pp.
6.Synthesis and properties of isomeric tris(N-[2-hydroxyethyl]ethylenediamine)cobalt(III)and tris(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。
发明内容
本发明旨在提供手性六[(R)-苯甘氨醇]氯化钴配合物。所要解决的技术问题是一步合成得到目标产物。
本发明所称的手性钴配合物是由六水合氯化钴与D-苯甘氨醇制备的由以下化学式所示的化合物：
化学名称：六[(R)-苯甘氨醇]氯化钴配合物,简称配合物(I)。
该配合物在苯甲醛的亨利反应中显示了一定的催化性能，其转化率达
本合成方法包括合成和分离，称取8.9005g(64.9mmol)L-苯甘氨醇放入100ml圆底烧瓶中，加入50ml氯苯，搅拌使其溶解，将2.3794g(31.2mmol)CoCl2·6H2O及5.0Ml的甲基苯基二氯硅烷加入上述溶液，加热回流48h，旋转出去溶剂，加入石油醚、二氯甲烷配制饱和溶液溶液，静置自然挥发，析出红棕色晶体。
合成反应如下：
本合成方法一步得到目标产物，工艺简单，操作方便。
附图说明
图1是手性六[(S)-苯甘氨醇]氯化钴配合物的单晶X-衍射图。
具体实施方式
手性六[(S)-苯甘氨醇]氯化钴配合物的制备：
称取4.1154g(0.03mol)D-苯甘氨醇放入100mL圆底烧瓶中，加入50mL无水甲醇，搅拌使其溶解；将2.3794g(0.01mol)的CoCl2·6H2O加入上述溶液，加热回流48h；趁热过滤反应溶液，静置于烧杯中自然挥发，得到紫红色晶体；产率：44％；m.p.:174-177℃；比旋光度为[α]20 D＝518.9°，(c 0.0030 CH3OH)元素分析数据为理论值(％)：C,49.95；H,5.76；N,7.28；实测值(％)：C,50.32；H,6.16；N,7.23。红外光谱数据(KBr；v；cm-1)3380，3120，2930，2860，2040，1620，1530，1450，1290，1190，1160,1060,849,769,700，650；
化合物的晶体数据：
晶体典型的键长数据：
晶体典型的键角数据
亨利反应应用
2-硝基-1-苯基乙醇
催化剂I(0.148mmol),苯甲醛0.10mL(0.986mmol)及硝基甲烷(0.50mL,9.255mmol)在室温下搅拌6h，用核磁监测，转化率：79.3％，1H NMR(300MHz,CDCl3)7.28～7.32(m,5H,Ar-H),5.32～5.35(d,J＝9.18Hz,1H,-CH),4.38～4.56(m,2H,-CH2),3.89(br,1H,-OH)。

Claims (3)

1.一种手性钴配合物(I)，其化学式如下：
2.权利要求1所述的手性钴配合物(I)，在293(2)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MoKα射线以ω-θ扫描方式收集衍射数据，单斜晶系,P2(1)2(1)2(1),α＝90°； β＝90°；γ＝90°。
3.权利要求1所述的手性钴配合物(I)的合成方法，本合成方法包括合成和分离，其特征在于：称取4.1154g D-苯甘氨醇放入100mL圆底烧瓶中，加入50mL无水甲醇，搅拌使其溶解；将2.3794g的CoCl2·6H2O加入上述溶液，加热回流48h；趁热过滤反应溶液，静置于烧杯中自然挥发，得到紫红色晶体。
CN201610409957.0A 2016-06-03 2016-06-03 一种钴配合物的制备及合成方法 Expired - Fee Related CN106083616B (zh)

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CN103570768A (zh) * 2013-11-15 2014-02-12 合肥工业大学 一种钴氮配合物
CN103613507A (zh) * 2013-10-26 2014-03-05 合肥工业大学 一种手性苯甘氨醇钴配合物
CN105237413A (zh) * 2015-10-30 2016-01-13 合肥祥晨化工有限公司 一种手性含结晶水苯甘氨醇钴配合物

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CN103613507A (zh) * 2013-10-26 2014-03-05 合肥工业大学 一种手性苯甘氨醇钴配合物
CN103570768A (zh) * 2013-11-15 2014-02-12 合肥工业大学 一种钴氮配合物
CN105237413A (zh) * 2015-10-30 2016-01-13 合肥祥晨化工有限公司 一种手性含结晶水苯甘氨醇钴配合物

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