CN102807504B - 一种水杨酰胺的合成方法 - Google Patents
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Abstract
一种水杨酰胺的合成方法，是邻羟基苯甲腈与D-苯甘氨醇在氯苯溶剂中有催化剂无水ZnCl2存在时于无水无氧条件下回流反应60~70小时，ZnCl2的用量为原料量的325mol%，反应结束后脱去氯苯、加30mL水搅拌溶解，再用氯仿萃取，萃取相经干燥、脱溶后上硅胶层析柱分离，用石油醚/二氯甲烷（体积比1：9）洗脱，收集最后组份点，脱去洗脱剂后得到目标产物水杨酰胺。
Description
一、技术领域
本发明涉及一种有机精细化学品的制备方法，确切地说是一种水杨酰胺的合成方法。
二、背景技术
水杨酰胺是解热镇痛药,用于发热头痛,神经痛,关节痛及活动性风湿症等。同时也是其它医药、农药等精细化学品的中间体。水杨酰胺的合成方法近几年已有许多文献报道，通常用催化剂由邻羟基苯甲腈加热水解后得到。【1-3】
参考文献：
1. Kiss, Arpad; Hell, Zoltan, A heterogeneous catalytic method for the conversion of nitriles into amides using molecular sieves modified with copper(II), Tetrahedron Letters, 2011 , 52(45), Pages 6021-6023.
2. By Garcia-Alvarez, Rocio et al, Arene-Ruthenium(II) Complexes Containing Inexpensive
Tris(dimethylamino)phosphine: Highly Efficient Catalysts for the Selective Hydration of Nitriles into
Amides , Organometallics, 2011, 30(20), 5442-5451.
3. Cadierno, Victorio et al, Bis(allyl)ruthenium(IV) Complexes Containing Water-Soluble Phosphane Ligands: Synthesis, Structure, and Application as Catalysts in the Selective Hydration of Organonitriles into Amides , 2010, Chemistry--A European Journal, 2010, 16(32), 9808-9817.
申请人在用一锅法合成噁唑啉-氯化锌配合物的实验中，意外地得到了另一种化合物水杨酰胺。
三、发明内容
本发明旨在提供化合物水杨酰胺，所要解决的技术问题是一步合成得到目标产物。
本合成方法包括合成和分离，所述的合成是邻羟基苯甲腈与D-苯甘氨醇在氯苯溶剂中有催化剂无水ZnCl2存在时于无水无氧条件下回流反应60~70小时，ZnCl2的用量为原料量的325 mol %。
反应结束后脱去氯苯、加30mL 水搅拌溶解，再用氯仿萃取，萃取相经干燥、脱溶后上硅胶层析柱分离，用石油醚/二氯甲烷（体积比1：9）洗脱，收集最后组份点，脱去洗脱剂后得到目标产物水杨酰胺。
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。
该反应机理可推测为邻腈在325Mmol% 的强路易斯酸二氯化锌作用下，遇水分子进行亲核加成反应，产物水杨酰胺。
四、附图说明
图1是水杨酰胺的X-衍射分析图。
五、具体实施方式
在100mL两口瓶中,无水无氧条件下,加入无水ZnCl2 4.3915g (32.29mmol),40ml氯苯, 3邻羟基苯甲腈1.1755g(9.878mmol), D-苯甘氨醇 4.1210 g, 将混合物在高温下回流72h,停止反应,减压以除去溶剂, ,将剩余物用30mL水溶解,并用CHCl3(20mLx2)萃取,有机相用无水硫酸钠干燥,旋转除去溶剂，上硅胶层析柱分离纯化，用石油醚/二氯甲烷（体积比1：9）混合液洗脱，收集最后组份点，脱去洗脱剂得到目标产物水杨酰胺。产率：20%；m.p.:139-142℃; 1HNMR (500MHz, CDCl3, 27℃), δ (ppm) = 6.84～7.71 (m, 4H), 5.96(s,2H)。IR (KBr, cm-1) : 3397(s), 1675(s), 1590(m), 1492(m), 1447(m), 1304(w), 1082(w), 951(w), 751(w); HRMS(EI):m/z (%): calcd for C7H7NO2: 137.0477; found:137.0481.
化合物的晶体结构测定：
在显微镜下选取合适大小的单晶在室温下进行X-射线单晶衍射实验，在293k温度下，在Oxford 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 A）以w-Theta 扫描方式收集衍射数据。对所得数据进行Lp因子及经验吸收校正，晶体结构由直接法解出，衍射数据还原和结构解析工作分别使用SAINT-5.0和SHELXS-97程序完成。晶体数据如下：
Empirical formula C7 H7 N O2
Formula weight 137.14
Temperature 293(2) K
Wavelength 0.71073 A
Crystal system, space group Monoclinic, C2/c
Unit cell dimensions a = 24.242(13) A alpha = 90 deg.
b = 4.954(3) A beta = 120.54(2) deg.
c = 12.824(9) A gamma = 90 deg.
Volume 1326.4(14) A^3
Z, Calculated density 8, 1.373 Mg/m^3
Absorption coefficient 0.102 mm^-1
F(000) 576
Crystal size 0.312 x 0.211 x 0.078 mm
Theta range for data collection 1.95 to 25.49 deg.
Limiting indices -21<=h<=28, -5<=k<=6, -15<=l<=13
Reflections collected / unique 3300 / 1166 [R(int) = 0.0637]
Completeness to theta = 25.49 95.3 %
Absorption correction Empirical
Max. and min. transmission 1.00000 and 0.37609
Refinement method Full-matrix least-squares on F^2
Data / restraints / parameters 1166 / 0 / 101
Goodness-of-fit on F^2 1.124
Final R indices [I>2sigma(I)] R1 = 0.0879, wR2 = 0.2571
R indices (all data) R1 = 0.0959, wR2 = 0.2643
Extinction coefficient 0.013(5)
Largest diff. peak and hole 0.345 and -0.256 e.A^-3
晶体的键长数据：
O(1)-C(1) 1.352(5)
O(2)-C(7) 1.248(4)
C(1)-C(6) 1.387(5)
C(1)-C(2) 1.388(6)
C(2)-C(3) 1.367(6)
C(3)-C(4) 1.371(6)
C(4)-C(5) 1.366(6)
C(5)-C(6) 1.400(5)
C(6)-C(7) 1.471(5)
晶体的键角数据
O(1)-C(1)-C(6) 122.0(3)
O(1)-C(1)-C(2) 117.6(3)
C(6)-C(1)-C(2) 120.4(3)
C(3)-C(2)-C(1) 120.2(4)
C(1)-C(6)-C(5) 117.9(3)
C(1)-C(6)-C(7) 119.4(3)
C(5)-C(6)-C(7) 122.8(3)
O(2)-C(7)-N(1) 119.7(3)
O(2)-C(7)-C(6) 120.2(3)
N(1)-C(7)-C(6) 120.1(3) 。
Claims (1)
1.一种水杨酰胺的合成方法，包括合成和分离，其特征在于：所述的合成是邻羟基苯甲腈与D-苯甘氨醇在氯苯溶剂中有催化剂无水ZnCl2存在时于无水无氧条件下回流反应60~70小时，ZnCl2的用量为原料量的325 mol %，反应结束后脱去氯苯、加30mL 水搅拌溶解，再用氯仿萃取，萃取相经干燥、脱溶后上硅胶层析柱分离，用石油醚/二氯甲烷（体积比1：9）洗脱，收集最后组份点，脱去洗脱剂后得到目标产物水杨酰胺。
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| CN105503640A (zh) * | 2015-12-31 | 2016-04-20 | 镇江高鹏药业有限公司 | 一种高效的水杨酰胺的制备方法 |
| CN109294308B (zh) * | 2018-10-10 | 2020-07-24 | 中国船舶重工集团公司第七二五研究所 | 一种柳酰胺锌螯合物及其制备方法 |
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Non-Patent Citations (8)
| Title |
|---|
| Á |
| & * |
| Aacute * |
| Maximilian N. Kopylovich,et al.Zinc(II)/Ketoxime System as a Simple and Efficient Catalyst for Hydrolysis of Organonitriles.《Inorg. Chem.》.2002,第41卷(第18期),4798-4804. |
| rpád Kiss, et al.A heterogeneous catalytic method for the conversion of nitriles into amides using molecular sieves modified with copper(II).《Tetrahedron Letters》.2011,第52卷6021-6023. * |
| Selective Ruthenium-Catalyzed Hydration of Nitriles to Amides in Pure Aqueous Medium Under Neutral Conditions;Victorio Cadierno, et al;《Chem. Eur. J.》;20080620;第14卷;6601 – 6605 * |
| Victorio Cadierno, et al.Selective Ruthenium-Catalyzed Hydration of Nitriles to Amides in Pure Aqueous Medium Under Neutral Conditions.《Chem. Eur. J.》.2008,第14卷6601 – 6605. |
| Zinc(II)/Ketoxime System as a Simple and Efficient Catalyst for Hydrolysis of Organonitriles;Maximilian N. Kopylovich,et al;《Inorg. Chem.》;20020802;第41卷(第18期);4798-4804 * |
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