CN114409684B - 一种手性氨基醇锌配合物的制备及用途 - Google Patents
一种手性氨基醇锌配合物的制备及用途 Download PDFInfo
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- -1 amino zinc alkoxide Chemical class 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000013078 crystal Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000706 filtrate Substances 0.000 claims abstract description 5
- 238000001308 synthesis method Methods 0.000 claims abstract description 5
- DMHGXMPXHPOXBF-UHFFFAOYSA-N 5-Methoxyisatin Chemical compound COC1=CC=C2NC(=O)C(=O)C2=C1 DMHGXMPXHPOXBF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000002447 crystallographic data Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 125000003580 L-valyl group Chemical group [H]N([H])[C@]([H])(C(=O)[*])C(C([H])([H])[H])(C([H])([H])[H])[H] 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- NWYYWIJOWOLJNR-RXMQYKEDSA-N l-valinol Chemical compound CC(C)[C@H](N)CO NWYYWIJOWOLJNR-RXMQYKEDSA-N 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 3
- 238000010992 reflux Methods 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZPPDPNQDTZPAER-UHFFFAOYSA-N 5-(2h-tetrazol-5-ylmethyl)-2h-tetrazole Chemical compound N1=NNN=C1CC=1N=NNN=1 ZPPDPNQDTZPAER-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 230000003872 anastomosis Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YCGAZNXXGKTASZ-UHFFFAOYSA-N thiophene-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)S1 YCGAZNXXGKTASZ-UHFFFAOYSA-N 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 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
- B01J31/22—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
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
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- 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
- C07C215/04—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 saturated
- C07C215/06—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 saturated and acyclic
- C07C215/08—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 saturated and acyclic with only one hydroxy group and one amino group bound to the carbon skeleton
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- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/10—Spiro-condensed systems
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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Abstract
Description
一、技术领域
本发明涉及一种新配合物及其用途,特别涉及一种锌配合物的制备及用途,确切地说是一种手性L-缬氨醇硝酸锌配合物的制备及用途。
二、背景技术
锌配合物是重要的催化剂和医药化工产品.其合成方法及用途见参考文献【1-3】:[1]韩佳星,刘峥,梁楚欣,et al.以吡啶-2,5-二羧酸或噻吩-2,5-二羧酸为配体的过渡金属配合物的合成、晶体结构及性质,无机化学学报,2019,35(04):605-12;[2]FREIS M,KLAPTKE T M,STIERSTORFER J,et al.Di(1H-tetrazol-5-yl)methane as Neutral Ligand inEnergetic Transition Metal Complexes[J].Inorganic chemistry,2017,56(14):7936-47;[3]AXELSON J C,GONZALEZ M I,MEIHAUS K R,et al.Synthesis andCharacterization of aTetrapodal NO44–Ligand and Its Transition MetalComplexes[J].Inorganic chemistry,2016,55(15):7527-34。
三、发明内容
本发明旨在提供含锌的配合物,所要解决的技术问题是一步合成得到目标产物。
本发明所称的锌配合物是由L-缬氨醇和六水合硝酸锌按摩尔比为3:1在无水甲醇溶液中制备的由以下化学式所示的配合物:
化学名称:含两分子结晶水的手性L-缬氨醇硝酸锌配合物,简称配合物(I)。
该配合物在5-甲氧基靛红的鲁卡特反应中显示了一定的催化性能,其转化率达81.4%。
本合成方法包括合成和分离,其合成方法是称取1.0487g L-缬氨醇、1.0115g六水合硝酸锌放入100mL圆底烧瓶,然后加入40mL无水甲醇作溶剂,加热搅拌回流48h后,热过滤,得无色滤液,静置自然挥发,7天后有无色晶体析出。
其合成反应如下:
本合成方法一步得到目标产物,工艺简单,操作方便。
该反应的反应机理可推测为三分子的手性配体L-缬氨醇化合物,在无水甲醇分子的作用下与六水合硝酸锌作用,一步形成含两分子结晶水的手性L-缬氨醇硝酸锌配合物.
四、附图说明
图1是含两分子结晶水的手性L-缬氨醇硝酸锌配合物的单晶X-衍射图。
五、具体实施方式
1.锌配合物的制备:
L-缬氨醇和六水合硝酸锌摩尔比为3:1参与反应,称取1.0487gL-缬氨醇、1.0115g六水合硝酸锌放入100mL圆底烧瓶,然后加入40mL无水甲醇作溶剂,加热搅拌回流48h,结束反应,热过滤,得无色滤液,静置自然挥发,7天后,有无色晶体析出。IR(KBr;ν,cm–1):3306,2968,1601,1522,1467,1325,1169,1030,1023,1090,881,834,825;产率:87%,m.p.:92–95℃;1H NMR(600MHz,CDCl3)1HNMR(600MHz,CDCl3,25℃),δ(ppm)=3.67-3.71(m,1H),3.22(t,1H),2.62(s,1H),2.52(t,1H),1.64-1.66(m,1H),0.89-0.95(dd,J=7.2Hz,6.6Hz,6H);13C NMR(150MHz,CDCl3),δ(ppm)=161.8,123.2,84.3,66.1,62.6,44.7,35.0,23.9;元素分析:C15H43N5O11Zn实测值为:C:33.86%;H:8.48%;N:13.45%。根据分子式计算的理论值为:C:33.65%;H:8.04%;N:13.09%;
化合物的晶体数据:
经验式 C15H43N5O11Zn
分子量 534.91
温度 293(2)K
晶系,空间群 单斜晶系,P21 21 21
电荷密度 4,1.306Mg/m^3
吸收校正参数 0.958mm^-1
单胞内的电子数目 1144
晶体大小 0.200x0.140x0.060mm
Theta角的范围 2.618 to 24.999°
HKL的指标收集范围 -8<=h<=12,-14<=k<15,-23<=l<=23
收集/独立衍射数据 10237/4664[R(int)=0.0899]
theta=30.5的数据完整度 97.1%
吸收校正的方法 多层扫描
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4664/10/305
精修使用的方法 1.007
衍射点的一致性因子 R1=0.1057,wR2=0.2590
可观察衍射的吻合因子 R1=0.1761,wR2=0.3214
晶体典型的键长数据:
晶体典型的键角数据
2.鲁卡特反应应用
目标合成的手性L-缬氨醇和六水合硝酸锌形成的配合物可作为催化剂应用于鲁卡特反应。鲁卡特反应是经典的有机反应之一。是合成喹唑啉衍生物化合物的方法之一。本实验的反应方程式:
称取5-甲氧基靛红0.08847g、甲酸铵0.26963g、1mmol%锌配合物I及无水甲醇5mL于25mL圆底烧瓶中,加热搅拌回流48h后,停止反应,旋转后,按石油醚:二氯甲烷1:1进行柱层分离,得晶体化合物,由核磁检测得其转化率:81.4%;1H NMR(600MHz,CDCl3),δppm10.0(s,1H),6.90-6.92(m,2H),6.85-6.87(m,3H),6.76(d,J=8.2Hz,1H),6.55(d,J=8.7Hz,1H),3.87(s,3H),3.73(d,J=7.3Hz,6H);13C NMR(150MHz,CDCl3)δppm 175.4,164.9(x2),158.8,155.6,151.3,140.3,134.4,134.3,121.9,115.5,115.4,112.7,111.7,111.3,111.1,56.0(x2),53.0。
Claims (3)
3.根据权利要求1所述的一种手性L-缬氨醇硝酸锌配合物的用途,所述的手性L-缬氨醇硝酸锌配合物I的合成方法包括合成和分离,所述的合成是称取1.0487g L-缬氨醇、1.0115g六水合硝酸锌放入100mL圆底烧瓶,然后加入40mL无水甲醇作溶剂,搅拌回流48h后,热过滤,得无色滤液,静置自然挥发,7天后有无色晶体析出。
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