[0001] 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。

[0002] 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 to 
chalcones 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。

[0003] 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)。

[0004] 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%。

[0005] 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。

[0006] 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。

[0007] 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。

[0008] 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]20D=-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-1
值（%）：C：48.54%；H：6.37%； N：10.57%；红外光谱数据（KBr；υ；cm ）：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

[0009] 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)。