CN105237413A - 一种手性含结晶水苯甘氨醇钴配合物 - Google Patents
一种手性含结晶水苯甘氨醇钴配合物 Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 4
- GUCGGMXQKFMTSU-UHFFFAOYSA-N [Co].NC(C1=CC=CC=C1)CO Chemical compound [Co].NC(C1=CC=CC=C1)CO GUCGGMXQKFMTSU-UHFFFAOYSA-N 0.000 title abstract 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 11
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000010992 reflux Methods 0.000 claims abstract description 4
- 239000012047 saturated solution Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- QMXOFBXZEKTJIK-UHFFFAOYSA-N Glycinol Natural products C1=C(O)C=C2OCC3(O)C4=CC=C(O)C=C4OC3C2=C1 QMXOFBXZEKTJIK-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 238000010189 synthetic method Methods 0.000 claims description 4
- 238000002447 crystallographic data Methods 0.000 claims description 2
- GUCGGMXQKFMTSU-QRPNPIFTSA-N [Co].N[C@H](C1=CC=CC=C1)CO Chemical compound [Co].N[C@H](C1=CC=CC=C1)CO GUCGGMXQKFMTSU-QRPNPIFTSA-N 0.000 claims 3
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 230000005260 alpha ray Effects 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 125000006850 spacer group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 6
- 238000005712 Baylis-Hillman reaction Methods 0.000 abstract description 3
- 150000002825 nitriles Chemical class 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 2
- IJXJGQCXFSSHNL-MRVPVSSYSA-N (2s)-2-amino-2-phenylethanol Chemical compound OC[C@@H](N)C1=CC=CC=C1 IJXJGQCXFSSHNL-MRVPVSSYSA-N 0.000 abstract 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 abstract 2
- 238000006842 Henry reaction Methods 0.000 abstract 1
- 238000006579 Tsuji-Trost allylation reaction Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 abstract 1
- 229910021332 silicide Inorganic materials 0.000 abstract 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- -1 water benzene glycinol cobalt complex Chemical class 0.000 description 9
- 230000009466 transformation Effects 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- CWKVFRNCODQPDB-UHFFFAOYSA-N 1-(2-aminoethylamino)propan-2-ol Chemical compound CC(O)CNCCN CWKVFRNCODQPDB-UHFFFAOYSA-N 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- LBFUKZWYPLNNJC-UHFFFAOYSA-N cobalt(ii,iii) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- HYWCXWRMUZYRPH-UHFFFAOYSA-N trimethyl(prop-2-enyl)silane Chemical compound C[Si](C)(C)CC=C HYWCXWRMUZYRPH-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
一种手性苯甘氨醇钴配合物（I），其化学式如下：（I）该手性苯甘氨醇钴配合物（I）的合成方法，是称取8.9005gL-苯甘氨醇放入100ml圆底烧瓶中，加入50ml氯苯，搅拌使其溶解，将2.3794gCoCl2·6H2O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，静置自然挥发，析出红棕色晶体；该配合物在苯甲醛的亨利反应，腈硅化反应，烯丙基烷基化反应及baylis-Hillman反应中显示了一定的催化性能，其转化率分别达48%，34%，53%及58%。
Description
一、技术领域
本发明涉及一种新化合物及其制备方法，特别涉及一种钴化合物及其制备方法，确切地说是一种手性含结晶水L-苯甘氨醇钴配合物的制备及合成方法。
二、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 conjugated systems. 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) complexes with 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-chelating aminoalcohols 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) complexes with amino alcohol ligands
Okamoto, Martha S. No Corporate
Source data available | (1974), 146 pp.
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。
三、发明内容
本发明旨在提供手性五水合六 [（S）-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甲基苯基二氯硅烷及L-苯甘氨醇制备的由以下化学式所示的化合物：
化学名称：五水合六[（S）-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，腈硅化反应，烯丙基烷基化反应及baylis-Hillman反应中显示了一定的催化性能，其转化率分别达48.3%，34%，53%及58%。
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。
四、附图说明
图1是手性五水合六[（S）-苯甘氨醇]氯化钴配合物的单晶X-衍射图。
五、具体实施方式
手性五水合六[（S）-苯甘氨醇]氯化钴配合物的制备：
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;元素分析C48H72Cl2Co3N6O11理论值（%）：理论值（%）：C：49.84% ; H: 6.27% ; N:
7.26%; 实测值（%）：C: 49.53%; H: 5.82%; N:
7.49%; 产率为92%;熔点为182-184℃，[a]5 D=-327.4º (c 0.134, CH3OH),
IR（KBr压片，cm-1）：3415,3291,3195,3062,2929,2854,
1586,1535, 1497, 1454, 1156, 1056,1011,760, 699.649,542,504;
化合物的晶体数据：
经验式
C48H72N6 O11Co3Cl2
分子量 1156.80’
温度
293(2) K
波长
0.71073 A
晶系， 空间群
单斜晶系, P2(1)2(1)2(1)
晶胞参数
a = 14.1410(18) Å alpha = 90deg.
b = 16.564 (2) Å beta = 90deg.
c = 23.383(3) A gamma = 90deg.
体积
5477.2（12）A^3
电荷密度
4, 1.403g/m^3
吸收 校正参数
1.056mm^-1
单胞内的电子数目
2420
晶体大小
0.210x 0.180x 0.13 mm
Theta 角的范围
1.683 to 25.500
HKL的指标收集范围
-17<=h<=10, -20<=k<19, -28<=l<=28
收集/独立衍射数据
30709/ 10194 [R(int) = 0.0909]
theta
= 30.5的数据完整度
99.9 %
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 10194/97/610
精修使用的方法
0.993
衍射点的一致性因子
R1 = 0.0622，wR2= 0.1361
可观察衍射的吻合因子
R1 = 0.1217, wR2 = 0.1653
绝对构型参数
0.042（14）
差值傅里叶图上的最大峰顶和峰谷 0.593
and -0.423e.A^-3
晶体典型的键长数据：
Co(1)-O(3)
2.085(7)
Co(1)-O(6)
2.088(7)
Co(1)-O(1)
2.093(6)
Co(1)-O(5)
2.094(6)
Co(1)-O(4)
2.108(6)
Co(1)-O(2)
2.149(6)
Co(1)-Co(3)
2.6393(18)
Co(1)-Co(2)
2.6475(18)
Co(2)-O(3)
1.900(6)
Co(2)-O(1)
1.904(6)
Co(2)-O(2)
1.910(6)
Co(2)-N(2)
1.936(8)
Co(2)-N(1)
1.941(9)
Co(2)-N(3)
1.947(8)
Co(3)-O(5)
1.892(6)
Co(3)-O(6)
1.911(6)
Co(3)-O(4)
1.919(6)
Co(3)-N(5)
1.933(7)
Co(3)-N(4)
1.936(7)
Co(3)-N(6)
1.945(7)
N(1)-C(2)
1.469(13)
N(1)-H(1A)
0.9700
N(1)-H(1B)
0.9700
N(2)-C(10)
1.483(13)
N(2)-H(2A)
0.9700
N(2)-H(2B)
0.9700
N(3)-C(18)
1.498(13)
N(3)-H(3A)
0.9700
N(3)-H(3B)
0.9700
N(4)-C(26)
1.479(11)
N(4)-H(4A)
0.9700
N(4)-H(4B)
0.9700
N(5)-C(34)
1.505(12)
N(5)-H(5A)
0.9700
N(5)-H(5B)
0.9700
N(6)-C(42)
1.493(12)
N(6)-H(6A)
0.9700
N(6)-H(6B)
0.9700
O(1)-C(1)
1.409(11)
O(1)-H(1)
0.9800
O(2)-C(9)
1.430(12)
O(3)-C(17)
1.427(11)
O(4)-C(25)
1.420(11)
O(5)-C(33)
1.406(11)
O(5)-H(5H)
0.9800
O(6)-C(41)
1.411(11)
O(7)-H(7A)
0.8302
O(7)-H(7B)
0.8396
O(8)-H(8A)
0.8173
O(8)-H(8B)
1.0017
O(9)-H(9C)
0.80(3)
O(9)-H(9D)
0.83(3)
O(10)-H(10B)
0.8297
O(10)-H(10A)
0.8279
O(11)-H(11A)
0.8496
C(1)-C(2)
1.509(14)
C(1)-H(1C)
0.9700
C(1)-H(1D)
0.9700
C(2)-C(3)
1.493(16)
C(2)-H(2)
0.9800
C(3)-C(4)
1.34(2)
C(3)-C(8)
1.380(18)
C(4)-C(5)
1.41(2)
C(4)-H(4)
0.9300
C(5)-C(6)
1.36(3)
C(5)-H(5)
0.9300
C(6)-C(7)
1.38(3)
C(6)-H(6)
0.9300
C(7)-C(8)
1.38(2)
C(7)-H(7)
0.9300
C(8)-H(8)
0.9300
C(9)-C(10)
1.500(14)
C(9)-H(9A)
0.9700
C(9)-H(9B)
0.9700
C(10)-C(11)
1.509(14)
C(10)-H(10)
0.9800
C(11)-C(16)
1.357(17)
C(11)-C(12)
1.367(15)
C(12)-C(13)
1.391(18)
C(12)-H(12)
0.9300
C(13)-C(14)
1.303(19)
C(13)-H(13)
0.9300
C(14)-C(15)
1.32(2)
C(14)-H(14)
0.9300
C(15)-C(16)
1.39(2)
C(15)-H(15)
0.9300
C(16)-H(16)
0.9300
C(17)-C(18)
1.477(14)
C(17)-H(17A)
0.9700
C(17)-H(17B)
0.9700
C(18)-C(19)
1.497(13)
C(18)-H(18)
0.9800
C(19)-C(20)
1.3900
C(19)-C(24)
1.3900
C(20)-C(21)
1.3900
C(20)-H(20)
0.9300
C(21)-C(22)
1.3900
C(21)-H(21)
0.9300
C(22)-C(23)
1.3900
C(22)-H(22)
0.9300
C(23)-C(24)
1.3900
C(23)-H(23)
0.9300
C(24)-H(24)
0.9300
C(25)-C(26)
1.518(13)
C(25)-H(25A)
0.9700
C(25)-H(25B)
0.9700
C(26)-C(27)
1.513(13)
C(26)-H(26)
0.9800
C(27)-C(32)
1.352(15)
C(27)-C(28)
1.380(16)
C(28)-C(29)
1.372(17)
C(28)-H(28)
0.9300
C(29)-C(30)
1.38(2)
C(29)-H(29)
0.9300
C(30)-C(31)
1.327(19)
C(30)-H(30)
0.9300
C(31)-C(32)
1.412(17)
C(31)-H(31)
0.9300
C(32)-H(32)
0.9300
C(33)-C(34)
1.495(13)
C(33)-H(33A)
0.9700
C(33)-H(33B)
0.9700
C(34)-C(35)
1.511(13)
C(34)-H(34)
0.9800
C(35)-C(40)
1.320(16)
C(35)-C(36)
1.389(15)
C(36)-C(37)
1.386(18)
C(36)-H(36)
0.9300
C(37)-C(38)
1.37(2)
C(37)-H(37)
0.9300
C(38)-C(39)
1.36(2)
C(38)-H(38)
0.9300
C(39)-C(40)
1.371(17)
C(39)-H(39)
0.9300
C(40)-H(40)
0.9300
C(41)-C(42)
1.499(14)
C(41)-H(41A)
0.9700
C(41)-H(41B)
0.9700
C(42)-C(43)
1.512(11)
C(42)-H(42)
0.9800
C(43)-C(44)
1.3900
C(43)-C(48)
1.3900
C(44)-C(45)
1.3900
C(44)-H(44)
0.9300
C(45)-C(46)
1.3900
C(45)-H(45)
0.9300
C(46)-C(47)
1.3900
C(46)-H(46)
0.9300
C(47)-C(48)
1.3900
C(47)-H(47)
0.9300
C(48)-H(48)
0.9300
晶体典型的键角数据
O(3)-Co(1)-O(6)
178.9(3)
O(3)-Co(1)-O(1)
75.7(3)
O(6)-Co(1)-O(1)
103.4(3)
O(3)-Co(1)-O(5)
104.2(2)
O(6)-Co(1)-O(5)
76.8(2)
O(1)-Co(1)-O(5)
176.3(3)
O(3)-Co(1)-O(4)
102.6(2)
O(6)-Co(1)-O(4)
77.1(2)
O(1)-Co(1)-O(4)
107.6(3)
O(5)-Co(1)-O(4)
76.1(2)
O(3)-Co(1)-O(2)
77.1(3)
O(6)-Co(1)-O(2)
103.3(3)
O(1)-Co(1)-O(2)
76.0(2)
O(5)-Co(1)-O(2)
100.3(2)
O(4)-Co(1)-O(2)
176.2(2)
O(3)-Co(1)-Co(3)
134.57(18)
O(6)-Co(1)-Co(3)
45.88(17)
O(1)-Co(1)-Co(3)
137.14(18)
O(5)-Co(1)-Co(3)
45.34(17)
O(4)-Co(1)-Co(3)
46.03(16)
O(2)-Co(1)-Co(3)
131.82(17)
O(3)-Co(1)-Co(2)
45.45(17)
O(6)-Co(1)-Co(2)
134.19(18)
O(1)-Co(1)-Co(2)
45.53(17)
O(5)-Co(1)-Co(2)
131.88(18)
O(4)-Co(1)-Co(2)
136.57(17)
O(2)-Co(1)-Co(2)
45.46(17)
Co(3)-Co(1)-Co(2)
176.87(7)
O(3)-Co(2)-O(1)
84.7(3)
O(3)-Co(2)-O(2)
87.7(3)
O(1)-Co(2)-O(2)
86.5(3)
O(3)-Co(2)-N(2)
174.7(3)
O(1)-Co(2)-N(2)
93.2(3)
O(2)-Co(2)-N(2)
87.3(3)
O(3)-Co(2)-N(1)
91.6(3)
O(1)-Co(2)-N(1)
87.1(3)
O(2)-Co(2)-N(1)
173.6(3)
N(2)-Co(2)-N(1)
93.2(4)
O(3)-Co(2)-N(3)
86.8(3)
O(1)-Co(2)-N(3)
170.5(3)
O(2)-Co(2)-N(3)
89.0(3)
N(2)-Co(2)-N(3)
94.9(4)
N(1)-Co(2)-N(3)
97.3(4)
O(3)-Co(2)-Co(1)
51.4(2)
O(1)-Co(2)-Co(1)
51.66(18)
O(2)-Co(2)-Co(1)
53.34(19)
N(2)-Co(2)-Co(1)
123.6(3)
N(1)-Co(2)-Co(1)
121.8(3)
N(3)-Co(2)-Co(1)
119.3(3)
O(5)-Co(3)-O(6)
86.2(3)
O(5)-Co(3)-O(4)
85.6(3)
O(6)-Co(3)-O(4)
86.1(3)
O(5)-Co(3)-N(5)
86.9(3)
O(6)-Co(3)-N(5)
173.1(3)
O(4)-Co(3)-N(5)
93.9(3)
O(5)-Co(3)-N(4)
172.9(3)
O(6)-Co(3)-N(4)
93.8(3)
O(4)-Co(3)-N(4)
87.4(3)
N(5)-Co(3)-N(4)
93.1(3)
O(5)-Co(3)-N(6)
91.3(3)
O(6)-Co(3)-N(6)
86.0(3)
O(4)-Co(3)-N(6)
171.7(3)
N(5)-Co(3)-N(6)
93.6(3)
N(4)-Co(3)-N(6)
95.7(3)
O(5)-Co(3)-Co(1)
51.91(18)
O(6)-Co(3)-Co(1)
51.7(2)
O(4)-Co(3)-Co(1)
52.24(18)
N(5)-Co(3)-Co(1)
123.5(2)
N(4)-Co(3)-Co(1)
123.2(2)
N(6)-Co(3)-Co(1)
120.2(2)
C(2)-N(1)-Co(2)
107.2(7)
C(2)-N(1)-H(1A)
110.3
Co(2)-N(1)-H(1A)
110.3
C(2)-N(1)-H(1B)
110.3
Co(2)-N(1)-H(1B)
110.3
H(1A)-N(1)-H(1B)
108.5
C(10)-N(2)-Co(2)
109.2(6)
C(10)-N(2)-H(2A)
109.8
Co(2)-N(2)-H(2A)
109.8
C(10)-N(2)-H(2B)
109.8
Co(2)-N(2)-H(2B)
109.8
H(2A)-N(2)-H(2B)
108.3
C(18)-N(3)-Co(2)
107.7(6)
C(18)-N(3)-H(3A)
110.2
Co(2)-N(3)-H(3A)
110.2
C(18)-N(3)-H(3B)
110.2
Co(2)-N(3)-H(3B)
110.2
H(3A)-N(3)-H(3B)
108.5
C(26)-N(4)-Co(3)
106.8(5)
C(26)-N(4)-H(4A)
110.4
Co(3)-N(4)-H(4A)
110.4
C(26)-N(4)-H(4B)
110.4
Co(3)-N(4)-H(4B)
110.4
H(4A)-N(4)-H(4B)
108.6
C(34)-N(5)-Co(3)
106.4(6)
C(34)-N(5)-H(5A)
110.5
Co(3)-N(5)-H(5A)
110.5
C(34)-N(5)-H(5B)
110.5
Co(3)-N(5)-H(5B)
110.5
H(5A)-N(5)-H(5B)
108.6
C(42)-N(6)-Co(3)
108.1(6)
C(42)-N(6)-H(6A)
110.1
Co(3)-N(6)-H(6A)
110.1
C(42)-N(6)-H(6B)
110.1
Co(3)-N(6)-H(6B)
110.1
H(6A)-N(6)-H(6B)
108.4
C(1)-O(1)-Co(2)
109.7(6)
C(1)-O(1)-Co(1)
124.2(6)
Co(2)-O(1)-Co(1)
82.8(2)
C(1)-O(1)-H(1)
112.1
Co(2)-O(1)-H(1)
112.1
Co(1)-O(1)-H(1)
112.1
C(9)-O(2)-Co(2)
108.3(6)
C(9)-O(2)-Co(1)
120.2(6)
Co(2)-O(2)-Co(1)
81.2(2)
C(17)-O(3)-Co(2)
109.0(6)
C(17)-O(3)-Co(1)
119.2(6)
Co(2)-O(3)-Co(1)
83.1(3)
C(25)-O(4)-Co(3)
108.9(5)
C(25)-O(4)-Co(1)
126.7(5)
Co(3)-O(4)-Co(1)
81.7(2)
C(33)-O(5)-Co(3)
110.2(5)
C(33)-O(5)-Co(1)
128.2(6)
Co(3)-O(5)-Co(1)
82.8(2)
C(33)-O(5)-H(5H)
110.6
Co(3)-O(5)-H(5H)
110.5
Co(1)-O(5)-H(5H)
110.5
C(41)-O(6)-Co(3)
109.7(5)
C(41)-O(6)-Co(1)
120.1(6)
Co(3)-O(6)-Co(1)
82.5(2)
H(7A)-O(7)-H(7B)
104.2
H(8A)-O(8)-H(8B)
80.4
H(9C)-O(9)-H(9D)
153(10)
H(10B)-O(10)-H(10A)
111.0
O(1)-C(1)-C(2)
109.1(8)
O(1)-C(1)-H(1C)
109.9
C(2)-C(1)-H(1C)
109.9
O(1)-C(1)-H(1D)
109.9
C(2)-C(1)-H(1D)
109.9
H(1C)-C(1)-H(1D)
108.3
N(1)-C(2)-C(3)
116.8(11)
N(1)-C(2)-C(1)
106.3(8)
C(3)-C(2)-C(1)
114.6(10)
N(1)-C(2)-H(2)
106.1
C(3)-C(2)-H(2)
106.1
C(1)-C(2)-H(2)
106.1
C(4)-C(3)-C(8)
116.7(15)
C(4)-C(3)-C(2)
123.0(14)
C(8)-C(3)-C(2)
120.2(15)
C(3)-C(4)-C(5)
122.9(18)
C(3)-C(4)-H(4)
118.6
C(5)-C(4)-H(4)
118.6
C(6)-C(5)-C(4)
117(2)
C(6)-C(5)-H(5)
121.3
C(4)-C(5)-H(5)
121.3
C(5)-C(6)-C(7)
122(2)
C(5)-C(6)-H(6)
118.9
C(7)-C(6)-H(6)
118.9
C(8)-C(7)-C(6)
117(2)
C(8)-C(7)-H(7)
121.6
C(6)-C(7)-H(7)
121.6
C(7)-C(8)-C(3)
124(2)
C(7)-C(8)-H(8)
118.1
C(3)-C(8)-H(8)
118.1
O(2)-C(9)-C(10)
110.0(9)
O(2)-C(9)-H(9A)
109.7
C(10)-C(9)-H(9A)
109.7
O(2)-C(9)-H(9B)
109.7
C(10)-C(9)-H(9B)
109.7
H(9A)-C(9)-H(9B)
108.2
N(2)-C(10)-C(9)
106.6(8)
N(2)-C(10)-C(11)
112.2(9)
C(9)-C(10)-C(11)
113.7(9)
N(2)-C(10)-H(10)
108.1
C(9)-C(10)-H(10)
108.1
C(11)-C(10)-H(10)
108.1
C(16)-C(11)-C(12)
116.7(12)
C(16)-C(11)-C(10)
120.5(11)
C(12)-C(11)-C(10)
122.8(10)
C(11)-C(12)-C(13)
121.5(13)
C(11)-C(12)-H(12)
119.2
C(13)-C(12)-H(12)
119.2
C(14)-C(13)-C(12)
120.0(16)
C(14)-C(13)-H(13)
120.0
C(12)-C(13)-H(13)
120.0
C(13)-C(14)-C(15)
120.5(16)
C(13)-C(14)-H(14)
119.8
C(15)-C(14)-H(14)
119.8
C(14)-C(15)-C(16)
121.1(16)
C(14)-C(15)-H(15)
119.5
C(16)-C(15)-H(15)
119.5
C(11)-C(16)-C(15)
120.2(16)
C(11)-C(16)-H(16)
119.9
C(15)-C(16)-H(16)
119.9
O(3)-C(17)-C(18)
110.0(9)
O(3)-C(17)-H(17A)
109.7
C(18)-C(17)-H(17A)
109.7
O(3)-C(17)-H(17B)
109.7
C(18)-C(17)-H(17B)
109.7
H(17A)-C(17)-H(17B)
108.2
C(17)-C(18)-N(3)
105.3(8)
C(17)-C(18)-C(19)
110.5(10)
N(3)-C(18)-C(19)
114.5(9)
C(17)-C(18)-H(18)
108.8
N(3)-C(18)-H(18)
108.8
C(19)-C(18)-H(18)
108.8
C(20)-C(19)-C(24)
120.0
C(20)-C(19)-C(18)
119.6(9)
C(24)-C(19)-C(18)
120.4(9)
C(21)-C(20)-C(19)
120.0
C(21)-C(20)-H(20)
120.0
C(19)-C(20)-H(20)
120.0
C(20)-C(21)-C(22)
120.0
C(20)-C(21)-H(21)
120.0
C(22)-C(21)-H(21)
120.0
C(23)-C(22)-C(21)
120.0
C(23)-C(22)-H(22)
120.0
C(21)-C(22)-H(22)
120.0
C(24)-C(23)-C(22)
120.0
C(24)-C(23)-H(23)
120.0
C(22)-C(23)-H(23)
120.0
C(23)-C(24)-C(19)
120.0
C(23)-C(24)-H(24)
120.0
C(19)-C(24)-H(24)
120.0
O(4)-C(25)-C(26)
108.7(7)
O(4)-C(25)-H(25A)
109.9
C(26)-C(25)-H(25A)
109.9
O(4)-C(25)-H(25B)
109.9
C(26)-C(25)-H(25B)
109.9
H(25A)-C(25)-H(25B)
108.3
N(4)-C(26)-C(25)
105.4(7)
N(4)-C(26)-C(27)
116.9(8)
C(25)-C(26)-C(27)
114.4(8)
N(4)-C(26)-H(26)
106.5
C(25)-C(26)-H(26)
106.5
C(27)-C(26)-H(26)
106.5
C(32)-C(27)-C(28)
117.8(11)
C(32)-C(27)-C(26)
122.9(10)
C(28)-C(27)-C(26)
119.3(10)
C(29)-C(28)-C(27)
122.0(13)
C(29)-C(28)-H(28)
119.0
C(27)-C(28)-H(28)
119.0
C(28)-C(29)-C(30)
119.7(14)
C(28)-C(29)-H(29)
120.2
C(30)-C(29)-H(29)
120.2
C(31)-C(30)-C(29)
118.8(13)
C(31)-C(30)-H(30)
120.6
C(29)-C(30)-H(30)
120.6
C(30)-C(31)-C(32)
121.9(13)
C(30)-C(31)-H(31)
119.1
C(32)-C(31)-H(31)
119.1
C(27)-C(32)-C(31)
119.9(12)
C(27)-C(32)-H(32)
120.1
C(31)-C(32)-H(32)
120.1
O(5)-C(33)-C(34)
109.0(8)
O(5)-C(33)-H(33A)
109.9
C(34)-C(33)-H(33A)
109.9
O(5)-C(33)-H(33B)
109.9
C(34)-C(33)-H(33B)
109.9
H(33A)-C(33)-H(33B)
108.3
C(33)-C(34)-N(5)
104.5(7)
C(33)-C(34)-C(35)
116.6(9)
N(5)-C(34)-C(35)
112.3(8)
C(33)-C(34)-H(34)
107.7
N(5)-C(34)-H(34)
107.7
C(35)-C(34)-H(34)
107.7
C(40)-C(35)-C(36)
115.9(11)
C(40)-C(35)-C(34)
125.5(11)
C(36)-C(35)-C(34)
118.6(11)
C(37)-C(36)-C(35)
120.7(13)
C(37)-C(36)-H(36)
119.7
C(35)-C(36)-H(36)
119.7
C(38)-C(37)-C(36)
120.3(14)
C(38)-C(37)-H(37)
119.8
C(36)-C(37)-H(37)
119.8
C(39)-C(38)-C(37)
119.1(15)
C(39)-C(38)-H(38)
120.4
C(37)-C(38)-H(38)
120.4
C(38)-C(39)-C(40)
118.3(15)
C(38)-C(39)-H(39)
120.9
C(40)-C(39)-H(39)
120.9
C(35)-C(40)-C(39)
125.6(13)
C(35)-C(40)-H(40)
117.2
C(39)-C(40)-H(40)
117.2
O(6)-C(41)-C(42)
108.5(8)
O(6)-C(41)-H(41A)
110.0
C(42)-C(41)-H(41A)
110.0
O(6)-C(41)-H(41B)
110.0
C(42)-C(41)-H(41B)
110.0
H(41A)-C(41)-H(41B)
108.4
N(6)-C(42)-C(41)
104.8(8)
N(6)-C(42)-C(43)
111.9(8)
C(41)-C(42)-C(43)
115.7(9)
N(6)-C(42)-H(42)
108.1
C(41)-C(42)-H(42)
108.1
C(43)-C(42)-H(42)
108.1
C(44)-C(43)-C(48)
120.0
C(44)-C(43)-C(42)
122.0(7)
C(48)-C(43)-C(42)
118.0(7)
C(45)-C(44)-C(43)
120.0
C(45)-C(44)-H(44)
120.0
C(43)-C(44)-H(44)
120.0
C(44)-C(45)-C(46)
120.0
C(44)-C(45)-H(45)
120.0
C(46)-C(45)-H(45)
120.0
C(47)-C(46)-C(45)
120.0
C(47)-C(46)-H(46)
120.0
C(45)-C(46)-H(46)
120.0
C(46)-C(47)-C(48)
120.0
C(46)-C(47)-H(47)
120.0
C(48)-C(47)-H(47)
120.0
C(47)-C(48)-C(43)
120.0
C(47)-C(48)-H(48)
120.0
C(43)-C(48)-H(48)
120.0
亨利反应应用:
2-
硝基
-1-
苯基乙醇
催化剂I (0.148mmol), 苯甲醛 0.10 mL (0.986 mmol) 及硝基甲烷(0.50 mL, 9.255 mmol) 在室温下搅拌 6 h，用核磁监测，转化率：48 %，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)。
腈硅化反应应用:
0.2mmol 配合物I, 苯甲醛0.1mL, TMSCN 0.3 ml
(3.3mmol), 2mL 无水甲醇, 相继在30~35˚C下加入，30小时后， 加入水淬灭经柱层后（石油醚/二氯甲烷：5/1），得无色油状液体, 转化率： 34%; 1H NMR
(300MHz, CDCl3) 7.56–7.59 (m, 0.9 Hz, 2H), 7.31–7.34 (m, 3H), 5.43 (s, 1H), 0.16 (s,
9H). 13C NMR (75 MHz, CDCl3) 136.1, 128.8(x2), 126.2(x2), 119.1,
63.5, -0.39(x3)。
烯丙基烷基化反应应用
取0.20mmol的配合物I(催化用量为20％)于25mL的小烧瓶中，加入2毫升的二氯甲烷溶液，然后，向上述溶液中加入0.1mL的苯甲醛与0.3mL的烯丙基三甲基硅烷，常温搅拌，反应72小时后，进行核磁分析，转化率：53％；1H NMR(300MHz,CDCl3)7.27～7.33(m,5H,Ar-H),5.79～5.80(m,1H),5.12～5.17(m,2H,-CH2),4.71(d，J＝5Hz，1H),2.49～2.50(m,2H)，2.28(s,1H)；
Baylis-Hillman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毫升的二氯甲烷溶液，然后，向上述溶液中加入0.1mL的苯甲醛与0.5mL丙烯酸甲酯，常温搅拌，反应72小时后，进行核磁分析，转化率：58％；1HNMR(300MHz,CDCl3)7.20～7.41(m,5H,Ar-H),6.30(s,1H),5.45(s,1H),3.70(s,3H),3.15(s,1H)。
Claims (3)
1.一种手性苯甘氨醇钴配合物（I），其化学式如下：
（I）
。
2.权利要求1所述的手性苯甘氨醇钴配合物（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λ=0.71073 Å，以ω-θ 扫描方式收集衍射数据，其特征在于晶体属斜方晶系,空间群 C2, a =
14.1734(4) Å ,α = 90°;b = 16.6428 (14) Å,β = 90°; c = 23.9849(19) Å, γ = 90°。
3.权利要求1所述的手性苯甘氨醇钴配合物（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8.9005gL-苯甘氨醇放入100ml圆底烧瓶中，加入50ml氯苯，搅拌使其溶解，将2.3794gCoCl2·6H2O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。
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| CN106083616A (zh) * | 2016-06-03 | 2016-11-09 | 合肥工业大学 | 一种钴配合物的制备及合成方法 |
| CN106220519A (zh) * | 2016-07-12 | 2016-12-14 | 合肥祥晨化工有限公司 | 一种钴配合物的制备及合成方法 |
| CN108840821A (zh) * | 2018-04-12 | 2018-11-20 | 合肥工业大学 | 一种钴配合物制备及其合成方法 |
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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 |
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| CN106083616A (zh) * | 2016-06-03 | 2016-11-09 | 合肥工业大学 | 一种钴配合物的制备及合成方法 |
| CN106083616B (zh) * | 2016-06-03 | 2018-01-26 | 合肥工业大学 | 一种钴配合物的制备及合成方法 |
| CN106220519A (zh) * | 2016-07-12 | 2016-12-14 | 合肥祥晨化工有限公司 | 一种钴配合物的制备及合成方法 |
| CN108840821A (zh) * | 2018-04-12 | 2018-11-20 | 合肥工业大学 | 一种钴配合物制备及其合成方法 |
| CN108840821B (zh) * | 2018-04-12 | 2021-05-25 | 合肥工业大学 | 一种钴配合物制备及其合成方法 |
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