CN107286039A - 一种酰胺晶体化合物的合成方法 - Google Patents
一种酰胺晶体化合物的合成方法 Download PDFInfo
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Abstract
一种有如下化学式（I）所示的酰胺晶体化合物:（Ⅰ）该酰胺晶体化合物（I）的合成方法，包括合成和分离，所述的合成是1.0ml苯甲醛与1.6516g苯甲酰胺在氯苯及四氢呋喃溶剂中有PdCl2存在时于无水无氧条件下回流反应24小时，PdCl2用量为原料量的5mol%反应停止后,有晶体出现。
Description
一、技术领域
本发明涉及一种化合物及其制备方法，特别涉及N，N’-（苯基亚甲基）二苯甲酰胺的合成方法。
二、背景技术
N，N’-（苯基亚甲基）二苯甲酰胺是重要的药物，可用做杀虫剂及抗癌药物，其合成方法已有大量文献报道【1-4】:
参考文献：
1. An efficient synthesis of symmetrical N,N-alkylidine bis-amidescatalysed by nano copper ferrite Organic Chemistry: An Indian Journal (2015),11, (9), 323-327.
2. N-Boc-aminals as easily accessible precursors for less accessible N-Boc-imines: facile synthesis of optically active propargylamine derivativesusing Mannich-type reactions Tetrahedron (2016).
3.Efficient synthesis of symmetrical N,N'-alkylidene bisamides catalysedby acetyl chloride Journal of Chemical Research (2013), 37, (12), 751-753.
4. A convenient synthesis of bisamides with BF3 etherate as catalystTetrahedron (2013), 69, (52), 11080-11083。
三、发明内容
本发明旨在为有机合成领域特别是制备药物提供一种手性化合物，所要解决的技术问题是遴选相应的原料并建立相应的方法合成化合物。
（一）本发明所称的化合物是以下化学式(Ⅰ)所合物：
（Ⅰ）。
其化学名称：N，N’-（苯基亚甲基）二苯甲酰胺，简称化合物（I）。
化合物（Ⅰ）的合成方法是苯甲醛与苯甲酰氨在有机溶剂四氢呋喃与氯苯于催化剂氯化钯5mol%存在条件下合成的，化学反应式如下：
本化合物(Ⅰ) 的合成方法包括合成、分离和纯化，所述的合成是1.0ml苯甲醛与1.6516g苯甲酰胺在氯苯及四氢呋喃溶剂中有PdCl2存在时于无水无氧条件下回流反应24小时，PdCl2用量为原料量的5mol%（摩尔百分比，下同）反应停止后,有晶体出现。
该反应的反应机理可推测如下：
苯甲醛与2分子的苯甲酰胺在路易斯酸的作用下缩合脱去一分子水，形成目标化合物I。
本化合物的制备，采用简易，高效的有机合成方法，一步合成化合物，经X-衍射，NMR,IR及元素分析确定其结构。
四、附图说明
图1是化合物 (I) 的单晶衍射图。
五、具体实施方式
1.N，N’-（苯基亚甲基）二苯甲酰胺的制备
在100mL两口瓶中,无水无氧条件下, 加入0.0080g氯化钯 , 20mL氯苯及20mLTHF,1.0mL 苯甲醛及1.6516g苯甲酰胺回流24h,停止反应后,有晶体出现：产率96%; m.p.232--234°C：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); 13CNMR(125MHz, CDCl3, 27℃),165.5(x2), 140.3,133.8,131.5,
128.3(x3),128.1(x3),127.6(x3),127.4(x3),126.4(x3),58.7;IR :3283, 3086，3061，3031, 2774, 1602, 1581, 1507, 1483, 1448, 1350, 1337, 1309, 1271, 1199,1180, 1139, 1088, 1077, 1062, 1048, 1030, 1001, 937, 874, 847, 780, 749, 696,666, 610, 589, 566, 486; HRMS(EI): m/z (%): calcd for C21H18N2O2: 330.1368;found: 330.1362，该配合物晶体数据如下：
经验式 C21H18N2O2
分子量 330.37
温度 100.01(10) K
波长 0.71073 A
晶系， 空间群 斜方晶系, P3(1)
晶胞参数 a = 17.0645(7) Å alpha = 90 deg.
b = 17.0645Å beta = 90 deg
c = 4.9440(2) Å gamma = 120 deg.
体积 1246.79(11)Å^3
电荷密度 4, 1.203Mg/m^3
吸收 校正参数 0.087mm^-1
单胞内的电子数目 472
晶体大小 0.25x 0.08x 0.05mm
Theta 角的范围 10.368 to 14
HKL的指标收集范围 -19<=h<=21, -16<=k<9, -5<=l<=5
收集/独立衍射数据 2723/2098[R(7int) = 0.0406]
theta = 30.5的数据完整度 1.133%
吸收校正的方法 多层扫描
最大最小的透过率 0.75and 0.34
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 2098/1/227
精修使用的方法 1.133
衍射点的一致性因子 R1 = 0.0579，wR2= 0.1505
可观察衍射的吻合因子 R1 = 0.6190, wR2 = 0.1535
绝对构型参数 0.2（8）
差值傅里叶图上的最大峰顶和峰谷 0.27 and -0.26e.A^-3
晶体典型的键长数据
| Atom | Atom | Length/Å | Atom | Atom | Length/Å | |
| O(1) | C(1) | 1.224(9) | C(9) | C(10) | 1.382(10) | |
| O(2) | C(15) | 1.230(9) | C(9) | C(14) | 1.392(10) | |
| N(1) | C(1) | 1.358(9) | C(10) | C(11) | 1.378(10) | |
| N(1) | C(8) | 1.460(8) | C(11) | C(12) | 1.389(12) | |
| N(2) | C(8) | 1.463(8) | C(12) | C(13) | 1.367(11) | |
| N(2) | C(15) | 1.350(8) | C(13) | C(14) | 1.389(10) | |
| C(1) | C(2) | 1.487(10) | C(15) | C(16) | 1.486(9) | |
| C(2) | C(3) | 1.387(12) | C(16) | C(17) | 1.402(11) | |
| C(2) | C(7) | 1.381(11) | C(16) | C(21) | 1.381(12) | |
| C(3) | C(4) | 1.379(12) | C(17) | C(18) | 1.370(13) | |
| C(4) | C(5) | 1.393(17) | C(18) | C(19) | 1.358(17) | |
| C(5) | C(6) | 1.343(16) | C(19) | C(20) | 1.359(18) | |
| C(6) | C(7) | 1.415(14) | C(20) | C(21) | 1.378(13) | |
| C(8) | C(9) | 1.529(9) |
晶体典型的键角数据：
| Atom | Atom | Atom | Angle/˚ | Atom | Atom | Atom | Angle/˚ | |
| C(1) | N(1) | C(8) | 119.9(6) | C(14) | C(9) | C(8) | 123.5(6) | |
| C(15) | N(2) | C(8) | 122.6(6) | C(11) | C(10) | C(9) | 121.3(7) | |
| O(1) | C(1) | N(1) | 122.7(7) | C(10) | C(11) | C(12) | 120.0(7) | |
| O(1) | C(1) | C(2) | 121.7(7) | C(13) | C(12) | C(11) | 119.3(7) | |
| N(1) | C(1) | C(2) | 115.6(6) | C(12) | C(13) | C(14) | 120.8(7) | |
| C(3) | C(2) | C(1) | 121.6(7) | C(13) | C(14) | C(9) | 120.2(6) | |
| C(7) | C(2) | C(1) | 119.9(7) | O(2) | C(15) | N(2) | 123.1(6) | |
| C(7) | C(2) | C(3) | 118.5(8) | O(2) | C(15) | C(16) | 121.6(6) | |
| C(4) | C(3) | C(2) | 121.4(9) | N(2) | C(15) | C(16) | 115.3(6) | |
| C(3) | C(4) | C(5) | 119.6(10) | C(17) | C(16) | C(15) | 122.6(7) | |
| C(6) | C(5) | C(4) | 120.0(8) | C(21) | C(16) | C(15) | 120.1(7) | |
| C(5) | C(6) | C(7) | 120.7(9) | C(21) | C(16) | C(17) | 117.3(7) | |
| C(2) | C(7) | C(6) | 119.8(9) | C(18) | C(17) | C(16) | 120.7(9) | |
| N(1) | C(8) | N(2) | 109.5(5) | C(19) | C(18) | C(17) | 121.1(11) | |
| N(1) | C(8) | C(9) | 112.9(5) | C(18) | C(19) | C(20) | 118.9(9) | |
| N(2) | C(8) | C(9) | 109.5(5) | C(19) | C(20) | C(21) | 121.5(10) | |
| C(10) | C(9) | C(8) | 118.2(6) | C(20) | C(21) | C(16) | 120.5(10) | |
| C(10) | C(9) | C(14) | 118.4(7) |
Claims (2)
1.一种有如下化学式（I）所示的酰胺晶体化合物:
（Ⅰ）
权利要求1所述的酰胺晶体化合物(I)，在100.01(10)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CuK\a射线（λ=1.54184Å）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, 斜方晶系, P3(1), 晶胞参数:a = 17.0645(7)Å alpha= 90 deg; b = 17.0645Å beta = 90 deg; c = 4.9440(2) Å gamma = 120 deg。
2.权利要求1所述的酰胺晶体化合物（I）的合成方法，包括合成和分离，所述的合成是1.0ml苯甲醛与1.6516g苯甲酰胺在氯苯及四氢呋喃溶剂中有PdCl2存在时于无水无氧条件下回流反应24小时，PdCl2用量为原料量的5mol% 反应停止后,有晶体出现。
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Non-Patent Citations (2)
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| 王宏社等: "二氧化硅负载高氯酸催化合成对称N,N′-亚烷基双酰胺", 《有机化学》 * |
| 袁承业等: "有机磷化合物的研究XXV.由N,N"-取代亚烷基双酰胺合成α-氨基膦酸", 《有机化学》 * |
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