CN107383111A - 一种手性镍配合物晶体及用途 - Google Patents
一种手性镍配合物晶体及用途 Download PDFInfo
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- CN107383111A CN107383111A CN201710596855.9A CN201710596855A CN107383111A CN 107383111 A CN107383111 A CN 107383111A CN 201710596855 A CN201710596855 A CN 201710596855A CN 107383111 A CN107383111 A CN 107383111A
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- 239000013078 crystal Substances 0.000 title claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 8
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000010189 synthetic method Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract 2
- STVVMTBJNDTZBF-SECBINFHSA-N (2r)-2-amino-3-phenylpropan-1-ol Chemical class OC[C@H](N)CC1=CC=CC=C1 STVVMTBJNDTZBF-SECBINFHSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 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
- STVVMTBJNDTZBF-VIFPVBQESA-N L-phenylalaninol Chemical compound OC[C@@H](N)CC1=CC=CC=C1 STVVMTBJNDTZBF-VIFPVBQESA-N 0.000 abstract 2
- 238000000034 method Methods 0.000 description 5
- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical class [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 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
- 239000003054 catalyst Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 description 1
- UHIJLWIHCPPKOP-UHFFFAOYSA-N [N].[Zn] Chemical class [N].[Zn] UHIJLWIHCPPKOP-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 150000001789 chalcones Chemical class 0.000 description 1
- 235000005513 chalcones Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- ZHDORMMHAKXTPT-UHFFFAOYSA-N n-benzoylbenzamide Chemical compound C=1C=CC=CC=1C(=O)NC(=O)C1=CC=CC=C1 ZHDORMMHAKXTPT-UHFFFAOYSA-N 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide 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
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- 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
- B01J2531/847—Nickel
-
- 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
- C07B2200/07—Optical isomers
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
一种手性二水合三[R‑(‑)‑苯丙氨醇]硝酸镍配合物镍配合物(I),其化学式如下:
Description
一、技术领域
本发明涉及一种新化合物及其制备方法,特别涉及一种镍化合物及其制备方法,确切地说是一种二水合三[R-(-)-苯丙氨醇]硝酸镍配合物的制备及合成方法。
二、背景技术
手性氨基醇镍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的加成反应中已显示了较好的催化性能。【1】
参考文献:
1. Catalytic enantioselective conjugate addition of diethylzinc tochalcones using chiral amino alcohol-nickel complexes, Wakimoto, Izumi;Tomioka, Yuko; Kawanami, Yasuhiro , Tetrahedron (2002), 58(40), 8095-8097。
三、发明内容
本发明旨在提供手性二水合三[R-(-)-苯丙氨醇]硝酸镍配合物; 所要解决的技术问题是一步合成得到目标产物。
本发明所称的手性锌配合物是由R-(-)-苯丙氨醇与六水合硝酸镍(Ⅱ)制备的由以下化学式所示的化合物:
(I)。
化学名称:二水合三[R-(-)-苯丙氨醇]硝酸镍配合物,简称配合物(I)。该配合物在苯甲醛与苯甲酰胺的反应中显示了一定的催化性能,其转化率达46%。
本合成方法包括合成和分离,称取D-苯丙氨醇3.0060 g(0.0199mol),六水合硝酸镍1.9271g(0.0066mol)于100mL圆底烧瓶,加入50mL无水甲醇作溶剂,加热搅拌回流36h,热过滤,静置挥发。数天后析出蓝色晶体;用石油醚和正己烷冲洗3次,真空干燥后,得到干净的目标产物。
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是二水合三[R-(-)-苯丙氨醇]硝酸镍配合物的单晶X-衍射图。
五、具体实施方式
二水合三[R-(-)-苯丙氨醇]硝酸镍配合物的制备:
D-苯丙氨醇和六水合硝酸镍以摩尔比3:1比例进行反应,称取D-苯丙氨醇3.0060 g(0.0199mol),六水合硝酸镍1.9271g(0.0066mol)于100mL圆底烧瓶,加入50mL无水甲醇作溶剂,加热搅拌回流36h,热过滤,静置挥发。数天后析出蓝色晶体;用石油醚和正己烷冲洗3次,真空干燥后,得到干净的目标产物,熔点为162~168℃。比旋光度为[α]20 D=-576.87°(c=0.080,CH3OH)。元素分析数据:C27H43N5NiO11,理论值(%):C:48.23%;H:6.45%;N:10.42%;实测值(%):C:48.54%;H:6.37%; N:10.57%;红外光谱数据(KBr;υ;cm-1):3319,3254,2953,2426,1603,1497,1382,1038,828,755,700,669;
配合物的晶体数据:
经验式 C27H43N5O11Ni
分子量 672.37
温度 293(2) K
波长 0.71073 Å
晶系, 空间群 单斜,P212121
晶胞参数 a = 10.0390(10) Å α = 90 °.
b = 13.2501 (12 Å β = 90 °.
c = 25.249(2) Å γ = 120 °.
体积 3358.6(6)Å^3
电荷密度 4, 1.330 Mg/m^3
吸收 校正参数 0.639 mm^-1
单胞内的电子数目 1424
晶体大小 0.220x 0.170x 0.140 mm
Theta 角的范围 1.613 to 25.499°
HKL的指标收集范围 -12<=h<=10, -14<=k<16, -30<=l<=30
收集/独立衍射数据 19413/ 6236 [R(int) = 0.0468]
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 6236/61/409
精修使用的方法 1.035
衍射点的一致性因子 R1 = 0.0535,ωR2= 0.1329
可观察衍射的吻合因子 R1 = 0.0747, ωR2 = 0.1463
绝对构型参数 0.023(11)
差值傅里叶图上的最大峰顶和峰谷 0.433and -0.281e.Å^-3
晶体典型的键长数据:
Ni(1)-N(2) 2.045(5)
Ni(1)-N(1) 2.064(5)
Ni(1)-O(2) 2.086(4)
Ni(1)-N(3) 2.094(5)
Ni(1)-O(3) 2.094(4)
Ni(1)-O(1) 2.132(4)
N(1)-C(2) 1.478(7)
N(1)-H(1A) 0.9700
N(1)-H(1B) 0.9700
N(2)-C(11) 1.477(7)
N(2)-H(2A) 0.9700
N(2)-H(2B) 0.9700
N(3)-C(20) 1.490(8)
N(3)-H(3A) 0.9700
N(3)-H(3B) 0.9700
N(4)-O(6) 1.184(9)
N(4)-O(4) 1.190(10)
N(4)-O(5) 1.225(9)
N(5)-O(9) 1.231(8)
N(5)-O(7) 1.233(8)
N(5)-O(8) 1.239(8)
O(1)-C(1) 1.429(8)
O(1)-H(1F) 0.83(3)
O(2)-C(10) 1.440(7)
O(2)-H(2F) 0.81(3)
O(3)-C(19) 1.403(8)
O(3)-H(3F) 0.82(3)
O(10)-H(10D) 0.8337
O(10)-H(10E) 0.8653
O(11)-H(11D) 0.8214
O(11)-H(11E) 0.7436
C(1)-C(2) 1.495(9)
C(1)-H(1C) 0.9700
C(1)-H(1D) 0.9700
C(2)-C(3) 1.522(8)
C(2)-H(2) 0.9800
C(3)-C(4) 1.511(8)
C(3)-H(3C) 0.9700
C(3)-H(3D) 0.9700
C(4)-C(9) 1.384(13)
C(4)-C(5) 1.389(12)
C(5)-C(6) 1.360(12)
C(5)-H(5A) 0.9300
C(6)-C(7) 1.392(17)
C(6)-H(6) 0.9300
C(7)-C(8) 1.351(16)
C(7)-H(7A) 0.9300
C(8)-C(9) 1.425(12)
C(8)-H(8A) 0.9300
C(9)-H(9) 0.9300
C(10)-C(11) 1.494(10)
C(10)-H(10A) 0.9700
C(10)-H(10B) 0.9700
C(11)-C(12) 1.525(7)
C(11)-H(11) 0.9800
C(12)-C(13) 1.491(8)
C(12)-H(12A) 0.9700
C(12)-H(12B) 0.9700
C(13)-C(18) 1.347(13)
C(13)-C(14) 1.371(10)
C(14)-C(15) 1.382(12)
C(14)-H(14) 0.9300
C(15)-C(16) 1.347(16)
C(15)-H(15) 0.9300
C(16)-C(17) 1.378(16)
C(16)-H(16) 0.9300
C(17)-C(18) 1.401(13)
C(17)-H(17) 0.9300
C(18)-H(18) 0.9300
C(19)-C(20) 1.500(9)
C(19)-H(19A) 0.9700
C(19)-H(19B) 0.9700
C(20)-C(21) 1.515(8)
C(20)-H(20) 0.9800
C(21)-C(22) 1.503(9)
C(21)-H(21A) 0.9700
C(21)-H(21B) 0.9700
C(22)-C(23) 1.357(10)
C(22)-C(27) 1.385(10)
C(23)-C(24) 1.387(11)
C(23)-H(23) 0.9300
C(24)-C(25) 1.346(13)
C(24)-H(24) 0.9300
C(25)-C(26) 1.352(13)
C(25)-H(25) 0.9300
C(26)-C(27) 1.393(11)
C(26)-H(26) 0.9300
C(27)-H(27) 0.9300
晶体典型的键角数据:
N(2)-Ni(1)-N(1) 166.54(19)
N(2)-Ni(1)-O(2) 80.86(19)
N(1)-Ni(1)-O(2) 93.6(2)
N(2)-Ni(1)-N(3) 98.7(2)
N(1)-Ni(1)-N(3) 94.1(2)
O(2)-Ni(1)-N(3) 96.46(19)
N(2)-Ni(1)-O(3) 89.84(19)
N(1)-Ni(1)-O(3) 96.4(2)
O(2)-Ni(1)-O(3) 169.78(19)
N(3)-Ni(1)-O(3) 80.69(17)
N(2)-Ni(1)-O(1) 88.2(2)
N(1)-Ni(1)-O(1) 79.42(19)
O(2)-Ni(1)-O(1) 89.47(19)
N(3)-Ni(1)-O(1) 171.5(2)
O(3)-Ni(1)-O(1) 94.49(17)
C(2)-N(1)-Ni(1) 107.3(3)
C(2)-N(1)-H(1A) 110.3
Ni(1)-N(1)-H(1A) 110.3
C(2)-N(1)-H(1B) 110.3
Ni(1)-N(1)-H(1B) 110.3
H(1A)-N(1)-H(1B) 108.5
C(11)-N(2)-Ni(1) 109.3(3)
C(11)-N(2)-H(2A) 109.8
Ni(1)-N(2)-H(2A) 109.8
C(11)-N(2)-H(2B) 109.8
Ni(1)-N(2)-H(2B) 109.8
H(2A)-N(2)-H(2B) 108.3
C(20)-N(3)-Ni(1) 106.2(3)
C(20)-N(3)-H(3A) 110.5
Ni(1)-N(3)-H(3A) 110.5
C(20)-N(3)-H(3B) 110.5
Ni(1)-N(3)-H(3B) 110.5
H(3A)-N(3)-H(3B) 108.7
O(6)-N(4)-O(4) 119.8(9)
O(6)-N(4)-O(5) 121.0(9)
O(4)-N(4)-O(5) 118.8(8)
O(9)-N(5)-O(7) 120.1(7)
O(9)-N(5)-O(8) 120.4(7)
O(7)-N(5)-O(8) 119.3(8)
C(1)-O(1)-Ni(1) 112.1(4)
C(1)-O(1)-H(1F) 116(5)
Ni(1)-O(1)-H(1F) 113(5)
C(10)-O(2)-Ni(1) 110.5(4)
C(10)-O(2)-H(2F) 128(7)
Ni(1)-O(2)-H(2F) 121(7)
C(19)-O(3)-Ni(1) 111.7(4)
C(19)-O(3)-H(3F) 116(4)
Ni(1)-O(3)-H(3F) 114(4)
H(10D)-O(10)-H(10E) 78.3
H(11D)-O(11)-H(11E) 170.7
O(1)-C(1)-C(2) 107.8(5)
O(1)-C(1)-H(1C) 110.1
C(2)-C(1)-H(1C) 110.1
O(1)-C(1)-H(1D) 110.1
C(2)-C(1)-H(1D) 110.1
H(1C)-C(1)-H(1D) 108.5
N(1)-C(2)-C(1) 107.4(5)
N(1)-C(2)-C(3) 112.3(5)
C(1)-C(2)-C(3) 112.9(6)
N(1)-C(2)-H(2) 108.0
C(1)-C(2)-H(2) 108.0
C(3)-C(2)-H(2) 108.0
C(4)-C(3)-C(2) 112.3(5)
C(4)-C(3)-H(3C) 109.1
C(2)-C(3)-H(3C) 109.1
C(4)-C(3)-H(3D) 109.1
C(2)-C(3)-H(3D) 109.1
H(3C)-C(3)-H(3D) 107.9
C(9)-C(4)-C(5) 120.5(8)
C(9)-C(4)-C(3) 121.8(8)
C(5)-C(4)-C(3) 117.7(8)
C(6)-C(5)-C(4) 123.2(12)
C(6)-C(5)-H(5A) 118.4
C(4)-C(5)-H(5A) 118.4
C(5)-C(6)-C(7) 114.1(13)
C(5)-C(6)-H(6) 123.0
C(7)-C(6)-H(6) 123.0
C(8)-C(7)-C(6) 126.9(11)
C(8)-C(7)-H(7A) 116.5
C(6)-C(7)-H(7A) 116.5
C(7)-C(8)-C(9) 116.9(12)
C(7)-C(8)-H(8A) 121.5
C(9)-C(8)-H(8A) 121.5
C(4)-C(9)-C(8) 118.2(12)
C(4)-C(9)-H(9) 120.9
C(8)-C(9)-H(9) 120.9
O(2)-C(10)-C(11) 106.9(5)
O(2)-C(10)-H(10A) 110.3
C(11)-C(10)-H(10A) 110.3
O(2)-C(10)-H(10B) 110.3
C(11)-C(10)-H(10B) 110.3
H(10A)-C(10)-H(10B) 108.6
N(2)-C(11)-C(10) 107.2(5)
N(2)-C(11)-C(12) 112.3(5)
C(10)-C(11)-C(12) 112.9(6)
N(2)-C(11)-H(11) 108.1
C(10)-C(11)-H(11) 108.1
C(12)-C(11)-H(11) 108.1
C(13)-C(12)-C(11) 114.4(5)
C(13)-C(12)-H(12A) 108.7
C(11)-C(12)-H(12A) 108.7
C(13)-C(12)-H(12B) 108.7
C(11)-C(12)-H(12B) 108.7
H(12A)-C(12)-H(12B) 107.6
C(18)-C(13)-C(14) 119.3(7)
C(18)-C(13)-C(12) 118.7(7)
C(14)-C(13)-C(12) 121.8(6)
C(13)-C(14)-C(15) 122.8(9)
C(13)-C(14)-H(14) 118.6
C(15)-C(14)-H(14) 118.6
C(16)-C(15)-C(14) 116.6(11)
C(16)-C(15)-H(15) 121.7
C(14)-C(15)-H(15) 121.7
C(15)-C(16)-C(17) 122.5(11)
C(15)-C(16)-H(16) 118.8
C(17)-C(16)-H(16) 118.8
C(16)-C(17)-C(18) 118.9(12)
C(16)-C(17)-H(17) 120.5
C(18)-C(17)-H(17) 120.5
C(13)-C(18)-C(17) 119.4(11)
C(13)-C(18)-H(18) 120.3
C(17)-C(18)-H(18) 120.3
O(3)-C(19)-C(20) 111.7(6)
O(3)-C(19)-H(19A) 109.3
C(20)-C(19)-H(19A) 109.3
O(3)-C(19)-H(19B) 109.3
C(20)-C(19)-H(19B) 109.3
H(19A)-C(19)-H(19B) 107.9
N(3)-C(20)-C(19) 106.7(5)
N(3)-C(20)-C(21) 113.9(5)
C(19)-C(20)-C(21) 113.2(6)
N(3)-C(20)-H(20) 107.6
C(19)-C(20)-H(20) 107.6
C(21)-C(20)-H(20) 107.6
C(22)-C(21)-C(20) 114.2(5)
C(22)-C(21)-H(21A) 108.7
C(20)-C(21)-H(21A) 108.7
C(22)-C(21)-H(21B) 108.7
C(20)-C(21)-H(21B) 108.7
H(21A)-C(21)-H(21B) 107.6
C(23)-C(22)-C(27) 116.7(7)
C(23)-C(22)-C(21) 122.7(7)
C(27)-C(22)-C(21) 120.6(6)
C(22)-C(23)-C(24) 121.7(8)
C(22)-C(23)-H(23) 119.2
C(24)-C(23)-H(23) 119.2
C(25)-C(24)-C(23) 120.2(9)
C(25)-C(24)-H(24) 119.9
C(23)-C(24)-H(24) 119.9
C(24)-C(25)-C(26) 120.5(9)
C(24)-C(25)-H(25) 119.7
C(26)-C(25)-H(25) 119.7
C(25)-C(26)-C(27) 118.9(9)
C(25)-C(26)-H(26) 120.6
C(27)-C(26)-H(26) 120.6
C(22)-C(27)-C(26) 121.9(8)
C(22)-C(27)-H(27) 119.1
C(26)-C(27)-H(27) 119.1
N,N’-(苯基亚甲基)二苯甲酰胺的制备
在25mL两口瓶中,加入15mol% 配合物I , 氯苯10mL, 0.1mL苯甲醛及0.2034g苯甲酰胺,回流反应21小时后,有晶体出现; 用核磁检测,转化率:46% ; 1HNMR (500MHz, CDCl3,27℃), δ (ppm) = 9.02 (d,J=7.77Hz, 2H), 7.91 (d, J=7.42Hz, 4H),7.54(t,J=7.4Hz, 2H),7.47 (t, J=7.7Hz, 6H), 7.37 (t,J=7.7Hz, 2H), 7.30 (t, J=7.3Hz,1H), 7.03(t, J=7.9Hz, 1H)。
Claims (4)
1.一种手性二水合三[R-(-)-苯丙氨醇]硝酸镍配合物镍配合物(I),其化学式如下:
(I)。
2.权利要求1所述的配合物晶体(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MoKa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 单斜, P212121 ;晶胞参数 : a = 10.0390(10) Å α = 90 °.;b = 13.2501(12 Å β = 90 °;c = 25.249(2) Å γ = 120 °。
3.权利要求2所述的配合物晶体(I)的合成方法,包括合成和分离,其特征在于所述的合成称取D-苯丙氨醇3.0060 g(0.0199mol),六水合硝酸镍1.9271g(0.0066mol)于100mL圆底烧瓶,加入50mL无水甲醇作溶剂,加热搅拌回流36h,热过滤,静置挥发。数天后析出蓝色晶体。
4.权利要求2所述的配合物晶体(I),该配合物在苯甲醛与苯甲酰胺的反应中显示了一定的催化性能,其转化率达46%。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102731539A (zh) * | 2012-07-12 | 2012-10-17 | 罗梅 | 一种手性化合物的制备及合成方法 |
CN103304586A (zh) * | 2013-07-07 | 2013-09-18 | 罗梅 | 一种手性铜配合物 |
CN103342710A (zh) * | 2013-07-29 | 2013-10-09 | 罗梅 | 一种手性锌配合物 |
CN103450034A (zh) * | 2013-09-22 | 2013-12-18 | 罗梅 | 一种手性镍配合物 |
CN103570562A (zh) * | 2013-11-17 | 2014-02-12 | 罗梅 | 一种手性镍配合物 |
CN103588821A (zh) * | 2013-10-16 | 2014-02-19 | 合肥工业大学 | 一种手性苯甘氨醇镍配合物 |
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102731539A (zh) * | 2012-07-12 | 2012-10-17 | 罗梅 | 一种手性化合物的制备及合成方法 |
CN103304586A (zh) * | 2013-07-07 | 2013-09-18 | 罗梅 | 一种手性铜配合物 |
CN103342710A (zh) * | 2013-07-29 | 2013-10-09 | 罗梅 | 一种手性锌配合物 |
CN103450034A (zh) * | 2013-09-22 | 2013-12-18 | 罗梅 | 一种手性镍配合物 |
CN103588821A (zh) * | 2013-10-16 | 2014-02-19 | 合肥工业大学 | 一种手性苯甘氨醇镍配合物 |
CN103570562A (zh) * | 2013-11-17 | 2014-02-12 | 罗梅 | 一种手性镍配合物 |
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