CN105566357A - 一种手性l-缬氨酸铜配合物的制备及合成方法 - Google Patents

一种手性l-缬氨酸铜配合物的制备及合成方法 Download PDF

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CN105566357A
CN105566357A CN201610146624.3A CN201610146624A CN105566357A CN 105566357 A CN105566357 A CN 105566357A CN 201610146624 A CN201610146624 A CN 201610146624A CN 105566357 A CN105566357 A CN 105566357A
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valine
copper complex
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罗梅
张志军
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Hefei Xiangchen Chemical Engineering Co Ltd
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Abstract

一种手性L-缬氨酸铜配合物晶体，其化学式如下：

Description

一种手性L-缬氨酸铜配合物的制备及合成方法
一、技术领域
本发明涉及一种新化合物，特别涉及一种手性化合物，确切地说是一种手性L-缬氨酸铜配合物的制备及合成方法。
二、背景技术
手性一水合二[L-缬氨酸]铜配合物在医药及生物领域有重要的用途，类似该化合物的结构已有文献报道[1-2]:
1.Synthesis, antimicrobial activity and cyclic voltammogram of Cu(II)complex , Li, Qiu-tong; Bo, Ying-ying; Xu, Xing-you; Duanmu, Chuan-song;Chen, Zhi-dong , Changzhou Daxue Xuebao, Ziran Kexueban (2012), 24(3), 75-79.
2.Synthesis, characterization and superoxide-​dismutase-​like activity ofCu(II) complex of L-
isoleucinate, Liao, Shengrong; Lin, Qingbin; Le, Xueyi; Feng, XiaolongHuaxue
Yanjiu (2006), 17(1), 9-12.
三、发明内容
本发明旨在提供手性一水合二[L-缬氨酸]铜配合物。所要解决的技术问题是一步合成得到目标产物。
本发明所称的一水合二[L-缬氨酸]铜配合物的制备是由L-缬氨酸与二水合氯化铜作用，由以下化学式所示的化合物：
（I）。
化学名称：一水合二[L-缬氨酸]铜配合物,简称配合物(I)。
本合成方法包括合成和分离，所述的合成是称取1.7259g（0.015mol）L-缬氨酸放入100mL圆底烧瓶中，加入40mL无水甲醇并搅拌使其溶解；将0.9051g（0.05mol）二水合氯化铜加入上述溶液，加热回流48h；反应结束后趁热过滤反应溶液，将滤渣用20mL无水甲醇和20mL蒸馏水溶解，自然挥发，几天后有蓝色晶体析出；将蓝色晶体用石油醚和正己烷冲洗3次，真空干燥30min，得目标产物。
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。
该手性一水合二[L-缬氨酸]铜配合物在苯甲醛的腈硅化反应及丙酮酸乙酯的亨利反应中显示了较好的催化效果，其转化率分别为82%及90%。
四、附图说明
图1一水合二[L-缬氨酸]铜配合物的X-衍射分析图。
五、具体实施方式
称取1.7259g（0.015mol）L-缬氨酸放入100mL圆底烧瓶中，加入40mL无水甲醇并搅拌使其溶解；将0.9051g（0.05mol）二水合氯化铜加入上述溶液，加热回流48h；反应结束后趁热过滤反应溶液，将滤渣用20mL无水甲醇和20mL蒸馏水溶解，自然挥发，几天后有蓝色晶体析出。产率为31%，m.p.: >200°C, [α]20 D=-271.0°(c=0.0644，CH3OH)。元素分析数据Cu[C10H22N2O5]，理论值（%）：C：38.27%；H：7.07%；N：8.93%；实测值（%）：C：37.89%；H：7.01%；N：8.87%；红外光谱数据(KBr, cm-1)： 588， 645，794，923，1128，1382，1491，1621，2955，3289；
晶体结构数据：
经验式 C10H22 Cl2 N3 O5 Cu
分子量 313.83
温度 293(2) K
波长 0.71073 A
晶系， 空间群 单斜晶系,C2
晶胞参数 a = 21.376(5) Å α = 90°.
b = 9.686(3) Å β = 108.804(5) °.
c= 7.4209(19) Å γ = 90 °.
体积 1439.5(6）Å^3
电荷密度 4,1.448 Mg/m^3
吸收 校正参数 1.531 mm^-1
单胞内的电子数目 660
晶体大小 0.210 x 0.160 x 0.120 mm
Theta 角的范围 2.013 to 25.996°
HKL的指标收集范围 -26<=h<=17, -11<=k<11, -9<=l<=9
收集/独立衍射数据 4275 / 2525 [R(int) = 0.0363]
theta = 30.5的数据完整度 99.6 %
吸收校正的方法 多层扫描
最大最小的透过率 0.7456 and 0.5507
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 2525/95/196
精修使用的方法 1.047
衍射点的一致性因子 R1 = 0.0505，wR2= 0.1184
可观察衍射的吻合因子 R1 = 0.0555 wR2 = 0.1221
绝对构型参数 0.007（19）
差值傅里叶图上的最大峰顶和峰谷 0.735and -0.303e.A^-3
晶体典型的键长数据：
Cu(1)-O(2) 1.944(6)
Cu(1)-O(4) 1.954(6)
Cu(1)-N(2) 1.991(6)
Cu(1)-N(1) 2.001(7)
Cu(1)-O(5) 2.354(4)
N(1)-C(2) 1.492(11)
N(1)-H(1A) 0.9700
N(1)-H(1B) 0.9700
N(2)-C(7) 1.473(11)
N(2)-H(2A) 0.9700
N(2)-H(2B) 0.9700
O(1)-C(1) 1.237(11)
O(2)-C(1) 1.270(10)
O(3)-C(6) 1.227(10)
O(4)-C(6) 1.258(11)
O(5)-H(5D) 0.8110
O(5)-H(5F) 0.9271
C(1)-C(2) 1.516(15)
C(2)-C(3) 1.525(15)
C(2)-H(2) 0.9800
C(3)-C(5) 1.459(16)
C(3)-C(4) 1.470(16)
C(3)-H(3) 0.9800
C(4)-H(4A) 0.9600
C(4)-H(4B) 0.9600
C(4)-H(4C) 0.9600
C(5)-H(5A) 0.9600
C(5)-H(5B) 0.9600
C(5)-H(5C) 0.9600
C(6)-C(7) 1.527(9)
C(7)-C(8) 1.492(18)
C(7)-C(8') 1.607(19)
C(7)-H(7) 0.9800
C(8)-C(10) 1.52(2)
C(8)-C(9) 1.52(2)
C(8)-H(8) 0.9800
C(9)-H(9A) 0.9600
C(9)-H(9B) 0.9600
C(9)-H(9C) 0.9600
C(10)-H(10A) 0.9600
C(10)-H(10B) 0.9600
C(10)-H(10C) 0.9600
C(8')-C(9') 1.51(2)
C(8')-C(10') 1.54(2)
C(8')-H(8') 0.9800
C(9')-H(9'1) 0.9600
C(9')-H(9'2) 0.9600
C(9')-H(9'3) 0.9600
C(10')-H(10D) 0.9600
C(10')-H(10E) 0.9600
C(10')-H(10F) 0.9600
晶体典型的键角数据：
O(2)-Cu(1)-O(4) 90.6(2)
O(2)-Cu(1)-N(2) 171.3(3)
O(4)-Cu(1)-N(2) 83.6(2)
O(2)-Cu(1)-N(1) 84.0(3)
O(4)-Cu(1)-N(1) 162.7(3)
N(2)-Cu(1)-N(1) 99.8(3)
O(2)-Cu(1)-O(5) 98.0(2)
O(4)-Cu(1)-O(5) 108.7(2)
N(2)-Cu(1)-O(5) 90.0(3)
N(1)-Cu(1)-O(5) 88.4(3)
C(2)-N(1)-Cu(1) 110.3(5)
C(2)-N(1)-H(1A) 109.6
Cu(1)-N(1)-H(1A) 109.6
C(2)-N(1)-H(1B) 109.6
Cu(1)-N(1)-H(1B) 109.6
H(1A)-N(1)-H(1B) 108.1
C(7)-N(2)-Cu(1) 110.9(5)
C(7)-N(2)-H(2A) 109.5
Cu(1)-N(2)-H(2A) 109.5
C(7)-N(2)-H(2B) 109.5
Cu(1)-N(2)-H(2B) 109.5
H(2A)-N(2)-H(2B) 108.0
C(1)-O(2)-Cu(1) 116.8(6)
C(6)-O(4)-Cu(1) 116.4(5)
Cu(1)-O(5)-H(5D) 126.0
Cu(1)-O(5)-H(5F) 104.6
H(5D)-O(5)-H(5F) 114.9
O(1)-C(1)-O(2) 123.9(9)
O(1)-C(1)-C(2) 118.3(8)
O(2)-C(1)-C(2) 117.7(8)
N(1)-C(2)-C(1) 110.0(7)
N(1)-C(2)-C(3) 116.5(9)
C(1)-C(2)-C(3) 111.3(9)
N(1)-C(2)-H(2) 106.1
C(1)-C(2)-H(2) 106.1
C(3)-C(2)-H(2) 106.1
C(5)-C(3)-C(4) 113.1(13)
C(5)-C(3)-C(2) 112.1(11)
C(4)-C(3)-C(2) 113.5(12)
C(5)-C(3)-H(3) 105.8
C(4)-C(3)-H(3) 105.8
C(2)-C(3)-H(3) 105.8
C(3)-C(4)-H(4A) 109.5
C(3)-C(4)-H(4B) 109.5
H(4A)-C(4)-H(4B) 109.5
C(3)-C(4)-H(4C) 109.5
H(4A)-C(4)-H(4C) 109.5
H(4B)-C(4)-H(4C) 109.5
C(3)-C(5)-H(5A) 109.5
C(3)-C(5)-H(5B) 109.5
H(5A)-C(5)-H(5B) 109.5
C(3)-C(5)-H(5C) 109.5
H(5A)-C(5)-H(5C) 109.5
H(5B)-C(5)-H(5C) 109.5
O(3)-C(6)-O(4) 122.9(8)
O(3)-C(6)-C(7) 119.6(8)
O(4)-C(6)-C(7) 117.5(8)
N(2)-C(7)-C(8) 119.5(11)
N(2)-C(7)-C(6) 109.2(7)
C(8)-C(7)-C(6) 115.7(11)
N(2)-C(7)-C(8') 107.3(10)
C(6)-C(7)-C(8') 105.7(10)
N(2)-C(7)-H(7) 103.5
C(8)-C(7)-H(7) 103.4
C(6)-C(7)-H(7) 103.2
C(7)-C(8)-C(10) 109.1(16)
C(7)-C(8)-C(9) 107.3(15)
C(10)-C(8)-C(9) 114.0(19)
C(7)-C(8)-H(8) 108.8
C(10)-C(8)-H(8) 108.8
C(9)-C(8)-H(8) 108.8
C(8)-C(9)-H(9A) 109.5
C(8)-C(9)-H(9B) 109.5
H(9A)-C(9)-H(9B) 109.5
C(8)-C(9)-H(9C) 109.5
H(9A)-C(9)-H(9C) 109.5
H(9B)-C(9)-H(9C) 109.5
C(8)-C(10)-H(10A) 109.5
C(8)-C(10)-H(10B) 109.5
H(10A)-C(10)-H(10B) 109.5
C(8)-C(10)-H(10C) 109.5
H(10A)-C(10)-H(10C) 109.5
H(10B)-C(10)-H(10C) 109.5
C(9')-C(8')-C(10') 109.0(16)
C(9')-C(8')-C(7) 117.0(16)
C(10')-C(8')-C(7) 110.5(16)
C(9')-C(8')-H(8') 106.6
C(10')-C(8')-H(8') 106.6
C(7)-C(8')-H(8') 106.6
C(8')-C(9')-H(9'1) 109.5
C(8')-C(9')-H(9'2) 109.5
H(9'1)-C(9')-H(9'2) 109.5
C(8')-C(9')-H(9'3) 109.5
H(9'1)-C(9')-H(9'3) 109.5
H(9'2)-C(9')-H(9'3) 109.5
C(8')-C(10')-H(10D) 109.5
C(8')-C(10')-H(10E) 109.5
H(10D)-C(10')-H(10E) 109.5
C(8')-C(10')-H(10F) 109.5
H(10D)-C(10')-H(10F) 109.5
H(10E)-C(10')-H(10F) 109.5
腈硅化反应应用
2-苯基-2-（三甲硅氧基）丙腈
0.0314g（0.1mmol）L-缬氨酸铜配合物（Ⅷ），再加入2mL 四氢呋喃、0.3mL 三甲基硅腈和0.1mL苯甲醛，常温搅拌72h后，进行1HNMR检测, 转化率：82 %; 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). 13CNMR (75 MHz, CDCl3) 136.1, 128.8(x2), 126.2(x2), 119.1, 63.5, -0.39(x3)。
亨利反应应用
0.0235g（7.5%mmol）配合物（Ⅷ），置于25mL烧瓶中，依次加入0.5mL 苯甲醛, 1mL四氢呋喃、0.25mL硝基甲烷和0.015mL丙酮酸乙酯，常温搅拌反应6h，分别取样进行1HNMR检测,其转化率为90%; 1 H NMR (CDCl 3 ): δ=4.86 (d,J =13.8 Hz, 1H), 4.58 (d, J =13.8Hz, 1H), 4.34 (m, 2H), 3.85(s, 1H), 1.46 (s, 3H), 1.33 (t, J ) 7.2 Hz, 3H);13C NMR (CDCl 3 ):δ=173.4, 80.9, 72.4, 63.0, 23.8, 13.9。

Claims (3)

1.一种手性L-缬氨酸铜配合物晶体，其化学式如下：
（I）。
2.权利要求1所述的手性L-缬氨酸铜配合物晶体(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，其特征在于晶体属单斜晶系, C2；晶胞参数a = 21.376(5) Å α = 90°；b =9.686(3) Å β = 108.804(5) °；c = 7.4209(19) Å γ = 90 °。
3.权利要求1所述的手性L-缬氨酸铜配合物晶体(I)的合成方法，包括合成和分离，所述的合成所述的合成是称取1.7259g（0.015mol）L-缬氨酸放入100mL圆底烧瓶中，加入40mL无水甲醇，搅拌使其溶解；将0.9051g（0.05mol）二水合氯化铜加入上述溶液，加热回流48h；反应结束后趁热过滤反应溶液，将滤渣用20mL无水甲醇和20mL蒸馏水溶解，自然挥发，几天后有蓝色晶体析出；将蓝色晶体用石油醚和正己烷冲洗3次，真空干燥30min，得目标产物。
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