CN112047982A - 一种辛可宁钴钙配合物 - Google Patents

一种辛可宁钴钙配合物 Download PDF

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CN112047982A
CN112047982A CN202011081329.7A CN202011081329A CN112047982A CN 112047982 A CN112047982 A CN 112047982A CN 202011081329 A CN202011081329 A CN 202011081329A CN 112047982 A CN112047982 A CN 112047982A
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cobalt
calcium complex
cinchonine
anhydrous
calcium
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罗梅
杨斐
汪岚
邹龙琦
马元睿
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Hefei University of Technology
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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    • C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract

一种辛可宁钴钙配合物，其结构式如下：
Figure DDA0002716268930000011
该钴钙配合物晶体(I)的合成方法，是无水无氧条件下，辛可宁1.0g和氯化钴0.4g及无水氯化钙0.8g，于60ml无水乙醇中加热回流36h。旋干，产物加入适量石油醚配饱和溶液，挥发溶剂得产物；该钴钙配合物晶体化合物(Ⅰ)的用途，是作为催化剂在乙酰脲与D‑缬氨醇的反应中显示了较好的催化性能，其转化率达99％。

Description

一种辛可宁钴钙配合物
一、技术领域
本发明涉及一种新化合物及其制备方法，特别涉及一种钴钙配合物及其制备方法，确切地说是一种辛可宁配合物的钴钙配合物的制备及合成方法。
二、背景技术
金属有机配合物是配位化学相当重要的一个分支，它与化学的几乎所有分支及生物学、材料学均有关。是现在有机化学中极为活跃的领域之一,已经广泛应用于有机合成反应中。20世纪60年代后期出现的使用配体与过渡金属络合物催化的合成反应大大加速了手性药物的研究。化学催化合成法的重要内容便是配体及含金属催化剂的设计,从而使反应具有高效和高对映选择性。近年来钴氮金属配合物在催化领域取得了较好的催化效果。
参考文献：
1.NCN-Pincer Cobalt Complexes Containing Bis(oxazolinyl)phenylLigands,Hosokawa,Satomi；Ito,Jun-ichi；Nishiyama,Hisao,Organometallics(2013),32(14),3980-3985；
2.Cyclopentadienyl 1,2-and 1,3-Disubstituted Cobalt SandwichCompounds{η5-[MeOC(O)]2C5H3}Co(η4-C4Ph4):Precursors for Sterically HinderedBidentate Chiral and Achiral Ligands,Singh,Nem；Elias,Anil J.,Organometallics(2012),31(5),2059-2065；
3.(Py)2Co(CH2SiMe3)2As an easily accessible source of"CoR2"，Zhu,Di；Janssen,Femke F.B.J.；Budzelaar,Peter H.M.,Organometallics(2010),29(8),1897-1908。
三、发明内容
本发明旨在提供一种钴钙金属有机配合物以应用于催化领域，所要解决的技术问题是遴选邻辛可宁配体并合成钴钙配合物。
本发明所称的钴钙配合物是由辛可宁1.0g和氯化钴0.4g及无水氯化钙0.8g制备的由以下化学式所示的配合物：
Figure BDA0002716268910000021
化学名称：辛可宁钴钙配合物,简称配合物(I)。
该配合物在乙酰脲与D-缬氨醇的反应中显示了较好的催化性能，其转化率达99％。
本合成方法包括合成和分离，所述的合成是辛可宁1.0g和氯化钴0.4g及无水氯化钙0.8g，于60ml无水乙醇中加热回流36h。旋干，产物加入适量石油醚配饱和溶液，挥发溶剂得产物。
其合成反应如下：
Figure BDA0002716268910000031
本合成方法一步得到目标产物，工艺简单，操作方便。
该配合物形成的反应机理可推测为辛克宁化合物与六水合氯化钴及无水氯化钙按一锅法反应，得到结构独特的钴钙配合物。
四、附图说明
图1是辛可宁钴钙配合物的X-衍射分析图。
五、具体实施方式
1.配合物的制备：
往烧瓶中加入辛可宁(1g，3.40mmol)和氯化钴(0.4g，7.69mmol)及氯化钙0.8g，再加入60ml无水乙醇。加热回流36h,旋干，产物加入适量石油醚配饱和溶液，挥发溶剂得产物0.2g；δH(600MHz,DMSO-d6,27℃),11.66(s,2H),8.94(s,3H),8.37(s,3H),8.10(s,3H),7.91(s,2H),6.94(s,2H),6.62(s,2H),6.02-6.08(m,5H),5.19-5.23(m,5H),4.10(s,3H),3.93-3.93(m,4H),3.40-3.50(m,3H),3.32-3.35(m,11H),3.15-3.18,(m,4H),2.63-2.64(m，3H),2.27-2.48(m,3H),1.92-2.00(m,4H),1.64-1.77(m,6H),1.54-1.56(m，1H)，1.22(s,3H),0.89-0.90(M,1H)；δc(150MHz,DMSO-d6)138.1,134.1,130.4,118.3,117.3,66.8,59.8,49.1,47.9,36.9,27.3,23.2,17.7,11.9；元素分析：实测值：C:49.51，H:5.59，N:5.85％；C57H70Ca2 Cl8Co2N6O5·2C2H5OH，理论值：C:49.07，H:5.54，N:5.63％；IR(KBr，ν，cm-1)：3412,2947,2800,2617,1628,1600,1386,1099,838,763,635；ESI:M+1/e:理论值：1401.0773；实测值：1401.0712；
配合物的晶体数据：
经验式 C57H70Ca2Cl8Co2N6O5
分子量 1400.81
温度 192(2)K
波长 0.71073A
晶系，空间群 单斜晶系,P 21
晶胞参数
Figure BDA0002716268910000041
α＝90°.
Figure BDA0002716268910000042
β＝97.044(3)°.
Figure BDA0002716268910000043
γ＝90°.
体积
Figure BDA0002716268910000044
电荷密度 2,1.387Mg/m^3
吸收校正参数 6.704mm^-1
单胞内的电子数目 1448
晶体大小 0.190x 0.160x 0.100mm
Theta角的范围 2.096 to 25.999
HKL的指标收集范围 -12<＝h<＝12,-16<＝k<16,-30<＝l<＝30
收集/独立衍射数据 50725/13175[R(int)＝0.0609]
吸收校正的方法 多层扫描
最大最小的透过率 0.7456and 0.5518
精修使用的方法 F^2的矩阵最小二乘法
数据数目/使用限制的数目/参数数目 13175/33/731
精修使用的方法 1.041
衍射点的一致性因子 R1＝0.0605，wR2＝0.1567
可观察衍射的吻合因子 R1＝0.0727,wR2＝0.1658
差值傅里叶图上的最大峰顶和峰谷 1.355and-0.763e.A^-
晶体典型的键长数据：
Figure BDA0002716268910000045
Figure BDA0002716268910000051
Figure BDA0002716268910000061
Figure BDA0002716268910000071
Figure BDA0002716268910000081
Figure BDA0002716268910000091
晶体典型的键角数据:
Figure BDA0002716268910000092
Figure BDA0002716268910000101
Figure BDA0002716268910000111
Figure BDA0002716268910000121
Figure BDA0002716268910000131
Figure BDA0002716268910000141
Figure BDA0002716268910000151
Figure BDA0002716268910000161
4-异丙基噁唑啉基-2-酮的制备
Figure BDA0002716268910000162
无水无氧条件下，用配合物1mmol做催化剂，称取乙酰脲2.0449g及1.3275g(D/L)缬氨醇8.1397g，放入250mL两口烧瓶中，加入100mL氯苯做溶剂，回流反应48小时后，柱层析分离，用石油醚/二氯甲烷(3/7)洗脱，将收集的第一组分点自然挥发，得单晶4-异丙基噁唑啉基-2-酮；转化率：>99％；1HNMR(500MHz,CDCl3,27℃),δ(ppm)＝7.08(br,1H),4.44(t,1H),4.08-4.12(m，1H),3.59-3.65(m，1H),3.64(t,J＝0.5Hz,1H),1.67～1.79(m,1H),0.92～0.99(dd,J＝6.6Hz,6.7Hz,6H),13CNMR(125MHz,CDCl3,27℃)160.7,68.6，58.4，32.7,18.0,17.6；IR(KBr):3273,2961,1753,1728,1473,1405，1328，1247，1091，1051，1009，936，901，769，711，550。

Claims (4)

1.一种辛可宁钴钙配合物，其特征是由以下化学式所示的化合物：
Figure FDA0002716268900000011
2.由权利要求1所述的钴钙配合物晶体(I)，在273(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单斜晶系,P21，晶胞参数：其晶胞参数：
Figure FDA0002716268900000012
Figure FDA0002716268900000013
β＝97.044(3)；
Figure FDA0002716268900000014
γ＝90°。
3.由权利要求1所述的钴钙配合物晶体(I)的合成方法，包括合成、分离和纯化，所述的合成是无水无氧条件下，辛可宁1.0g和氯化钴0.4g及无水氯化钙0.8g，于60ml无水乙醇中加热回流36h。旋干，产物加入适量石油醚配饱和溶液，挥发溶剂得产物。
4.由权利要求1所述的钴钙配合物晶体化合物(Ⅰ)的用途，是作为催化剂在乙酰脲与D-缬氨醇的反应中显示了较好的催化性能，其转化率达99％。
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103804429A (zh) * 2014-03-12 2014-05-21 罗梅 一种手性亮氨醇钴配合物
CN105712927A (zh) * 2016-01-21 2016-06-29 合肥工业大学 一种钴配合物制备及其合成方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103804429A (zh) * 2014-03-12 2014-05-21 罗梅 一种手性亮氨醇钴配合物
CN105712927A (zh) * 2016-01-21 2016-06-29 合肥工业大学 一种钴配合物制备及其合成方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LUOMEI ET AL.,: "Synthesis and Catalytic Activity of Nickel(II) and Cobalt(II) Complexes Involving Chiral Leucinol" *
LUOMEI ET AL.,: "Synthesis and Crystal Structure of Cobalt(II) and Copper(II) Complexes Involving L-Aamino Alcohols" *

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