CN112047891B - 一种2-羟基苯基-5-吡嗪基甲酮的合成方法及用途 - Google Patents

一种2-羟基苯基-5-吡嗪基甲酮的合成方法及用途 Download PDF

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CN112047891B
CN112047891B CN202010982583.8A CN202010982583A CN112047891B CN 112047891 B CN112047891 B CN 112047891B CN 202010982583 A CN202010982583 A CN 202010982583A CN 112047891 B CN112047891 B CN 112047891B
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Abstract

一种由以下化学式(I)所示的2‑羟基苯基‑5‑吡嗪基甲酮的合成方法，是称取钯配合物0.048g，0.8413g色酮‑3‑甲醛及甲酸铵2.5719g放入100mL圆底烧瓶中，再加入50mL无水甲醇溶解，加热回流36h后停止反应，用石油醚及二氯甲烷按体积比1:1柱层析，将第一组分点自然挥发后，得淡黄色晶体；该化合物的化学式如下：
Figure DDA0002688083030000011
该化合物(I)的用途，是作为催化剂在二苯亚胺与三甲基硅腈的反应中显示了良好的催化性能，其转化率高达69.1％。

Description

一种2-羟基苯基-5-吡嗪基甲酮的合成方法及用途
一、技术领域
本发明涉及一种化合物的制备方法，特别涉及一种吡嗪衍生物的合成方法及用途，确切地说是一种2-羟基苯基-5-吡嗪基甲酮的合成方法及用途。
二、背景技术
2-羟基苯基-5-吡嗪基甲酮的合成方法已被大量文献报道，见参考文献【1-3】：
参考文献：
1.Unusual transformation of substituted-3-formylchromones topyrimidine analogues:Synthesis and antimicrobial activities of 5-(o-hydroxyaroyl)pyrimidines,Raj,Tilak et al,Bioorganic&Medicinal ChemistryLetters,23(22),6093-6096；2013.
2.Synthesis of 5H-[1]benzopyrano[4,3-d]pyrimidin-5-one,Loewe,W.,Synthesis,(4),274；1976。
申请人以1mol％钯配合物作催化剂下，催化色酮-3-甲醛与甲酸铵的反应，用无水甲醇做溶剂，得到了一种化合物。所要解决的技术问题是一步合成得到目标产物。
(一)本发明所称的化合物是以下化学式(Ⅰ)所示的化合物：
Figure BDA0002688083010000011
其化学名称：2-羟基苯基-5-吡嗪基甲酮，简称化合物(I).
本化合物(I)的合成方法包括合成和分离，所述的合成是称取0.048g钯配合物，0.8413g色酮-3-甲醛及甲酸铵2.5719g放入100mL圆底烧瓶中，再加入50mL无水甲醇溶解，加热回流36h后停止反应，用石油醚及二氯甲烷按体积比1:1柱层析，将第一组分点自然挥发后，得淡黄色晶体。
合成反应如下：
Figure BDA0002688083010000012
本合成方法一步得到目标产物，工艺简单，操作方便。
其反应机理可推测如下：
色酮-3-甲醛仅在1mol％钯配合物作用下，首先环醚分解，再与及甲酸铵作用，一步反应得到2-羟基苯基-5-吡嗪基甲酮。
四、附图说明
图1 2-羟基苯基-5-吡嗪基甲酮的晶体X-衍射分析图。
五、具体实施方式
1.手性钯配合物的制备
(1)[1,4-(4R)-二异丙基－2－噁唑啉基]苯的制备
在100mL两口瓶中,无水无氧条件下,加入无水ZnCl21.4054g(10.64mmol),40ml氯苯,1,4-二氰基苯5.0236g(39.2mmol),L-缬氨醇16.2075g,将混合物在高温下回流60h,停止反应,减压以除去溶剂,,将剩余物用水溶解,并用CHCl3(20mLx2)萃取,有机相用无水硫酸钠干燥,旋转除去溶剂,将粗产品用石油醚/二氯甲烷(4:1)柱层析,得浅绿色粘稠状液体,产率52％；白色晶体,熔点:48-50℃,[a]5 D＝+111.9°(c＝0.429,CHCl3)；1HNMR(500MHz,CDCl3,27℃),δ(ppm)＝7.97(s,4H),4.39～4.43(t,3.18Hz,1H),4.09～4.15(m,2H),1.85～1.86(m,1H),(d,J＝6.24Hz,6H),0.86～0.96(d,J＝6.24Hz,6H).13CNMR 18.13,19.03,32.85,70.26,72.76,128.10,128.16,130.32,162.82.IR:3273,2976,2960,2932,2889,2869,1643,1512,1469,1408,1382,1366,1350,1320,1296,1276,1214,1180,1108,1077,1047,1014,971,955,900,891,838,726,698,675,659,540.HRMS(EI):m/z(％):calcd forC18H24N2O2:300.1838；found:300.1833。
(2)双{[1,4-(4S)-二异丙基－2－噁唑啉基苯]氯化钯}配合物的制备
100mL两口瓶中,无水无氧条件下,加入氯化钯1.5603g(4.92mmol),1,4-(4R)-二异丙基－2－噁唑啉基苯1.0435g(3.48mmol)，氯苯30mL将混合物在高温下回流48h,停止反应,减压以除去溶剂,,将剩余物三氯甲烷及乙醇溶解，自然挥发，得红褐色配合物得晶体，产率：92％；m.p.:>200℃,[a]5 D＝+512.8°(c 0.0564,CH3OH)；1H NMR(600MHz,CDCl3),δ`ppm8.81(s,8H,ArH),4.61-4.63(m,4H,CH×4),4.53(t,J＝9.6Hz,4H,CH×4),4.44(t,J＝8.5Hz,4H,CH×4),3.07-3.10(m,4H),1.18and 1.15(dd,J＝6.7,7.2Hz,24H,CH3×4)；13CNMR(150MHz,CDCl3)δppm 166.8,130.1(×2),129.3,72.0,69.1,30.7,19.0,15.6；νmax(cm-1)3487,3049,2957,2929,2872,1642,1609,1572,1509,1480,1464,1416,1379,1331,1288,1246,1178,1141,1123,1099,1045,1018,959,933,899,854,804,770,722,693,438；Elemental analysis for C36H48N4Cl4O4Pd2,found C 45.26％,H 5.06％,N 5.86％；requires C 45.32％,H 5.24％,N 5.48％；
2.2-羟基苯基-5-吡嗪基甲酮的制备
称取钯配合物0.048g，0.8413g色酮-3-甲醛及甲酸铵2.5719g放入100mL圆底烧瓶中，再加入50mL无水甲醇溶解，加热回流36h后停止反应，用石油醚及二氯甲烷按体积比1:1柱层析，将第一组分点自然挥发后，得淡黄色晶体。晶体(I):产率：52％；m.p:82-84℃；FTIR(cm-1)3408,3044,1621，1602，1574,1465，1432，1416，1335，1299，1242,1219，1191，1178，1149，1115，1035，1001，964，937，919，895，863，826，767,751，715，660，631，586；1H NMR(400MHz,DMSO-d6)δ10.6(s,1H,OH),9.32(s,1H),9.0(s,2H),7.48-7.49(m,2H),6.96-6.99(m,2H)；13C NMR(100MHz,DMSO-d6)δ161.66,161.24,134.64,130.69,129.10,128.78,115.83,115,36,84.03,83.82,55.19；Anal.Calcd.for C11H18N2O2:C,66.00；H,4.03；N,13.99.Found:C,65.87；H,4.38；N,13.65；HRMS for C11H18N2O2：Anal.Calcd.:200.0586；Found:200.0596；
该化合物晶体(I)的晶体数据如下：
Figure BDA0002688083010000031
Figure BDA0002688083010000041
晶体典型的键长数据：
Figure BDA0002688083010000042
晶体典型的键角数据：
Figure BDA0002688083010000043
Figure BDA0002688083010000051
二苯甲酮亚胺与三甲基硅腈的缩合反应应用
Figure BDA0002688083010000052
称取1mmol二苯甲酮亚胺和三甲基硅腈0.2mL放置于25mL小烧瓶中，加入2mLTHF及0.1mmol化合物I，常温下搅拌5h，取少量样品做核磁检测，转化率达:69.1％1H NMR(600MHz,CDCl3,27℃)δ7.23–7.59(m,10H),4.10(s,2H)。

Claims (2)

1.一种有 如下晶胞参数的由以下化学式(I)所示的2-羟基苯基-5-吡嗪基甲酮的合成方法，其特征在于：所述的合成是称取双{[1,4-(4S)-二异丙基－2－噁唑啉基苯]氯化钯}钯配合物0.048g，0.8413g色酮-3-甲醛及甲酸铵2.5719g放入100mL圆底烧瓶中，再加入50mL无水甲醇溶解，加热回流36h后停止反应，用石油醚及二氯甲烷按体积比1:1柱层析，将第一组分点自然挥发后，得淡黄色晶体；
该化合物的化学式如下：
Figure FDA0003240713950000011
其晶胞参数如下：在273(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CuKα射线
Figure FDA0003240713950000012
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,空间群:P 21 21 21；晶胞参数:
Figure FDA0003240713950000013
α＝90°；
Figure FDA0003240713950000014
β＝90°；
Figure FDA0003240713950000015
Figure FDA0003240713950000016
γ＝90°。
2.由权利要求1所述的化合物(I)的用途，其特征在于：作为催化剂在二苯亚胺与三甲基硅腈的反应中显示了良好的催化性能，其转化率高达69.1％。
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CN107353221A (zh) * 2017-07-13 2017-11-17 合肥祥晨化工有限公司 一种手性化合物的制备方法及用途
CN110669023A (zh) * 2019-10-17 2020-01-10 合肥工业大学 一种手性噁唑啉铜配合物的用途
CN111018776A (zh) * 2020-02-11 2020-04-17 合肥工业大学 一种吡啶衍生物的合成方法及用途

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107353221A (zh) * 2017-07-13 2017-11-17 合肥祥晨化工有限公司 一种手性化合物的制备方法及用途
CN110669023A (zh) * 2019-10-17 2020-01-10 合肥工业大学 一种手性噁唑啉铜配合物的用途
CN111018776A (zh) * 2020-02-11 2020-04-17 合肥工业大学 一种吡啶衍生物的合成方法及用途

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Unusual transformation of substituted-3-formylchromones to pyrimidine analogues: Synthesis and antimicrobial activities of 5-(o-hydroxyaroyl)pyrimidines;Tilak Raj et al.;《Bioorganic & Medicinal Chemistry Letters》;20130917;第23卷;第6093-6096页 *

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