CN103724212B - 一种手性(s)-苯乙胺盐酸盐氯化钴配合物晶体 - Google Patents
一种手性(s)-苯乙胺盐酸盐氯化钴配合物晶体 Download PDFInfo
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- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 title claims abstract description 13
- 229940097267 cobaltous chloride Drugs 0.000 title claims abstract description 13
- 229940048346 phenethylamine hydrochloride Drugs 0.000 title claims abstract description 13
- 239000013078 crystal Substances 0.000 title claims description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229940117803 phenethylamine Drugs 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 7
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000010189 synthetic method Methods 0.000 claims abstract description 5
- 238000000746 purification Methods 0.000 claims abstract description 4
- 238000001953 recrystallisation Methods 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract 2
- 238000002447 crystallographic data Methods 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- -1 hydrochloric acid Salt cobaltous chloride Chemical class 0.000 claims 1
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 abstract description 4
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 abstract description 2
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 abstract 2
- SKHIBNDAFWIOPB-UHFFFAOYSA-N hydron;2-phenylethanamine;chloride Chemical compound Cl.NCCC1=CC=CC=C1 SKHIBNDAFWIOPB-UHFFFAOYSA-N 0.000 abstract 2
- 239000000460 chlorine Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 238000006842 Henry reaction Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种手性(S)?苯乙胺盐酸盐氯化钴配合物,其化学式如下:
Description
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,特别涉及盐酸盐金属机配合物及其制备方法,确切地说是一种手性(S)-苯乙胺盐酸盐氯化钴配合物晶体的制备及合成方法。
二、背景技术
随着有机化学的发展,金属有机化合物在有机合成中的应用愈来愈广,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手性配体与过渡金属络合物催化的不对称合成反应大大加速了手性药物的研究。化学催化不对称合成法的重要内容便是手性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。本发明用一锅法合成了文献未曾报道的手性S-苯乙胺盐酸盐氯化钴配合物,而类似手性手性R-苯乙胺氯化铜配合物已有文献报道。【1-2】
参考文献:
1. The crystal structures of chiral (R/S) (C8H11N)2.CuCl2,Luo, Mei;Sun, Jie; Zhou, Shi-Ming; Yin, Hao; Hu, Ke-Liang,Research on ChemicalIntermediates (2010), 36(9), 1049-1054
2. Enantioselective henry reactions catalyzed by chiral N-metalcomplexes containing R(+)/S(-)-α-ethylphenyl amines, Luo, Mei; Yan, Bin,Tetrahedron Letters (2010), 51(42), 5577-5580。
三、发明内容
本发明旨在提供一种钴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(R)-苯乙胺作为配体并合成手性(S)-苯乙胺盐酸盐氯化钴配合物。
本发明所称的手性(S)-苯乙胺盐酸盐氯化钴配合物一种是由二苯基二氯硅烷、(S)-苯乙胺与六水合氯化钴制备的由以下化学式所示的配合物:
(Ⅰ)。
化学名称:手性(S)-苯乙胺盐酸盐氯化钴配合物,简称配合物(I)。
本合成方法包括合成和分离,所述的合成用25mmol六水合氯化钴, (S)-苯乙胺50mmol,二苯基二氯硅烷25mmol,用50mL氯苯做溶剂,回流反应72小时,纯化,即反应结束后脱去氯苯,用三氯甲烷/无水乙醇重结晶,得手性(S)-苯乙胺盐酸盐氯化钴配合物单晶。
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。
四、附图说明
图1手性(S)-苯乙胺盐酸盐氯化钴配合物的X-衍射分析图。
五、具体实施方式
在100mL两口瓶中,加入六水合氯化钴25mmol, 50mL氯苯,(S)-苯乙胺50mmol, 二苯基二氯硅烷25mmol, 将混合物在高温下回流72h,停止反应, 纯化,即反应结束后脱去氯苯,用三氯甲烷/无水乙醇重结晶,得手性(R)-苯乙胺盐酸盐氯化铜配合物单晶。产率88%,m.p.: 123-125°C,[a]5 D= -27.2 °(0.0736 , CH3OH),元素分析:测试值:C: 46.92%, H:5.82%, N: 7.14 %;计算值:46.84 %, H:5.83 %, N, 6.68 %;IR (KBr):3550, 3425,3111, 2934, 2568, 2452, 1593, 1486, 1457, 1386, 1316, 1290, 1224, 1168, 1086,1063, 1030, 970, 920, 767, 698;
配合物晶体数据如下:
经验式 C24H36 N3Cl5 Co
分子量 602.74
温度 293(2) K
波长 0.71073 A
晶系, 空间群 单斜晶系,P2(1)
晶胞参数 a = 14.061(2) A alpha = 90 deg.
b=7.5110(13) A beta= 98.685(4)deg.
c = 14.554 (3) A gamma = 90 deg.
体积 1519.4(5)A^3
电荷密度 2,1.317Mg/m^3
吸收 校正参数 1.021 mm^-1
单胞内的电子数目 626
晶体大小 0.211 x 0.121x 0.076mm
Theta 角的范围 1.88 to 25.05
HKL的指标收集范围 -16<=h<=15, -8<=k<=8, -16<=l<=17
收集/独立衍射数据 8034/ 5091 [R(int) = 0.0521]
theta = 30.5的数据完整度 99.9 %
吸收校正的方法 多层扫描
最大最小的透过率 1.0000 and 0.0983
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 5091/1/304
衍射点的一致性因子 R1 = 0.0859,wR2= 0.1989
可观察衍射的吻合因子 R1 = 0.0947, wR2 = 0.2028
绝对构型参数 0.10(4)
差值傅里叶图上的最大峰顶和峰谷 1.030 and -0.604e.A^-3
晶体典型的键长数据:
Co(1)-Cl(4) 2.250(3)
Co(1)-Cl(2) 2.257(2)
Co(1)-Cl(1) 2.276(3)
Co(1)-Cl(3) 2.287(2)
N(1)-C(1) 1.523(12)
N(1)-H(1A) 0.8900
N(1)-H(1B) 0.8900
N(1)-H(1C) 0.8900
N(2)-C(9) 1.463(13)
N(2)-H(2A) 0.8900
N(2)-H(2B) 0.8900
N(2)-H(2C) 0.8900
N(3)-C(17) 1.508(12)
N(3)-H(3A) 0.8900
N(3)-H(3B) 0.8900
N(3)-H(3C) 0.8900
晶体典型的键角数据:
Cl(4)-Co(1)-Cl(2) 110.72(11)
Cl(4)-Co(1)-Cl(1) 112.36(13)
Cl(2)-Co(1)-Cl(1) 110.91(10)
Cl(4)-Co(1)-Cl(3) 105.65(12)
Cl(2)-Co(1)-Cl(3) 110.35(10)
Cl(1)-Co(1)-Cl(3) 106.63(10)
C(1)-N(1)-H(1A) 109.5
C(1)-N(1)-H(1B) 109.5
H(1A)-N(1)-H(1B) 109.5
C(1)-N(1)-H(1C) 109.5
H(1A)-N(1)-H(1C) 109.5
H(1B)-N(1)-H(1C) 109.5
C(9)-N(2)-H(2A) 109.5
C(9)-N(2)-H(2B) 109.5
H(2A)-N(2)-H(2B) 109.5
C(9)-N(2)-H(2C) 109.5
H(2A)-N(2)-H(2C) 109.5
H(2B)-N(2)-H(2C) 109.5
C(17)-N(3)-H(3A) 109.5
C(17)-N(3)-H(3B) 109.5
H(3A)-N(3)-H(3B) 109.5
C(17)-N(3)-H(3C) 109.5
H(3A)-N(3)-H(3C) 109.5
H(3B)-N(3)-H(3C) 109.5
(六)、亨利反应应用
取0.20mmol的配合物I(催化用量为20%)于25mL的小烧瓶中,加入2毫升的无水甲醇溶液,然后,向上述溶液中加入0.1mL的苯甲醛与0.5mL的硝基甲烷,常温搅拌,反应72小时后,进行核磁分析,转化率:87.8 %;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(S)-苯乙胺盐酸盐氯化钴配合物,其化学式如下:
2.权利要求1所述的配合物(I),在273(2)k温度下,在Oxford X-射线单晶衍射仪上,用经石墨单色器单色化的MoKa射线以w-Theta扫描方式收集衍射数据,其特征在于晶体属单斜晶系,P2(1),空间群P2(1),α=90°;β=98.685(4)°;γ=90°。
3.权利要求1所述的配合物(I)的合成方法,包括合成和分离,所述的合成用25mmol六水合氯化钴,(S)-苯乙胺50mmol,二苯基二氯硅烷25mmol,用50mL氯苯做溶剂,回流反应72小时,纯化,即反应结束后脱去氯苯,用三氯甲烷/无水甲醇重结晶,得手性(S)-苯乙胺盐酸盐氯化钴配合物单晶。
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CN102688778A (zh) * | 2012-06-14 | 2012-09-26 | 罗梅 | 一种钴配合物的用途 |
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CN101830919A (zh) * | 2010-05-17 | 2010-09-15 | 合肥工业大学 | 一种手性α-苯乙胺的锌氮、铜氮配合物及其用途 |
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