CN115385946A - 亚氨基硼酸盐及其合成方法和用途 - Google Patents
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Abstract
本发明提供一类亚氨基硼酸盐化合物，该类化合物显示出良好的光物理性质，有望开发成新型荧光探针。本发明在乙腈中无催化剂条件下α‑羟基腙、水杨醛和硼酸衍生物作为起始材料，按照一锅法合成亚氨基硼酸盐化合物，所有产品均可通过过滤和洗涤快速纯化。
Description
本申请要求2022年07月06日提交的中国专利申请2022107908290的优先权，所述申请的内容均援引加入本文。
技术领域
本发明涉及亚氨基硼酸盐及其合成方法和用途。
背景技术
非侵害性细胞成像能使诊断变得容易，并监测细胞内环境中的生物结构和生理生化过程，已被大量研究证明是临床诊断和生物研究中不可缺少的的工具。因此，很多的细胞成像技术，如单光子发射计算机断层扫描、磁共振成像、正电子发射断层扫描和荧光探针技术等被广泛应用。其中，荧光探针技术因具有实时监测能力、良好的生物相容性、高灵敏度、高对比度、在细胞水平具有更高分辨率以及低成本等优点受到了广泛的关注。
发明内容
本发明提供一类亚氨基硼酸盐化合物，该类化合物显示出良好的光物理性质，有望开发成新型荧光探针。
一类亚氨基硼酸盐化合物，结构如下：
其中，R’为各自独立的氢，C1-C6的烷基或C1-C6的烷氧基，卤素、N,N二烷基；R为各自独立的氢，C1-C6的烷基或C1-C6的烷氧基，卤素、一个或多个卤素取代的甲基、硝基、羟基。
所述C1-C6烷基是指甲基、乙基、丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、新戊基、正己基或异己基；所述C1-C6的烷氧基是指甲氧基或乙氧基；所述卤素是氟、氯、溴或碘。N,N二烷基是指N,N二甲基或N,N二乙基。
R’可以独立的为邻位、间位或对位，可以邻位、间位和对位同时取代，也可以单独取代。R可以独立的为邻位、间位或对位，可以邻位、间位和对位同时取代，也可以单独取代。
所述式9化合物选自9a-9h化合物：
上述式9化合物合成路线如下：
反应溶剂选自四氢呋喃、甲醇、乙腈、N,N-二甲基甲酰胺、丙酮、乙酸乙酯中的一种或几种混合，优选乙酸乙酯或乙腈。反应温度为80℃。
上述式9化合物作为荧光探针中的应用。
有益效果：
本发明提供一类亚氨基硼酸盐化合物，该类化合物显示出良好的光物理性质，有望开发成新型荧光探针。本发明在乙腈中无催化剂条件下α-羟基腙、水杨醛和硼酸衍生物作为起始材料，按照一锅法合成亚氨基硼酸盐化合物，所有产品均可通过过滤和洗涤快速纯化。本发明合成方法的优点包括无催化剂、反应时间短、易于后处理，以及它们能够适应广泛的底物，以及良好的产率。此外，通过简单的过滤和洗涤，可以方便地纯化产品。
附图说明
图1中(a)为9g化合物在各种溶剂中的吸收光谱(1×10-5M)；(b)为9g化合物在各种溶剂中的发射光谱(1×10-6M)。
图2中(a)为9a-9e化合物(1×10-5M)、9f化合物(4×10-6M)和9g化合物(1× 10-6M)在乙腈中的吸收光谱；(b)为9a-9e化合物(1×10-5M)、9f化合物(4× 10-6M)和9g化合物(1×10-6M)在乙腈中的荧光光谱(λex＝295nm)。
具体实施方式
下面通过具体实施例对本发明进行具体描述，在此指出以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，本领域的技术熟练人员可以根据上述发明内容对本发明作出一些非本质的改进和调整。
实施例1
反应路线：
操作步骤：
向圆底烧瓶中加入2-羟基苯乙酮(14.7mmol，1.0equiv)、80％水合肼(17.6 mmol，1.2equiv)和乙醇(15mL)。将所得混合物在常温下搅拌并保持15小时。当反应完成时，然后减压除去溶剂。随后，用乙醇和石油醚混合溶剂重结晶，即得目标化合物6。
实施例2
反应路线：
操作步骤：
将α-羟基肼6(1.0mmol，1.0equiv)、水杨醛8(1.0mmol，1.0equiv)、苯硼酸2(1.2mmol，1.2equiv)衍生物和乙腈(2mL)在圆底烧瓶中混合在一起并在80℃搅拌和搅拌1小时。用TLC监测反应进程。一旦反应完成，将其冷却至室温。过滤后用甲醇洗涤，得到纯品。
本发明合成了一系列亚氨基硼酸盐化合物9a-9g。在过滤和洗涤后，所有最终产品均以中等收率获得。在这项研究中，发明人发现硼酸上的给电子基团或吸电子基团的存在对反应结果的影响很小，即使水杨醛具有给电子基团，反应也能顺利进行。遗憾的是，发明人选择了3,5-二氯水杨醛作为起始原料，但没有检测到产物9h。因此，取代基对水杨醛的电效应对反应结果有明显的影响。
结果与讨论
亚氨基硼酸盐合成的底物范围
光物理性质
发明人研究了新合成的产物9a-9g的光物理性质。给出了在不同极性的各种溶剂中测量的亚氨基硼酸盐9g的吸收和发射光谱以进行比较(图1)。相比之下，发明人未能检测到任何溶剂化变色。然而，随着溶剂极性的增加，发射波长 (λem)发生红移，荧光强度降低。
此外，在乙腈中对化合物9a-9g进行了紫外-可见和荧光光谱测量(所有光物理参数列于表1)。在紫外-可见光谱分析中，吸收光谱呈现一到两个波段，主波段在302-425nm之间。水杨醛中的给电子取代基(-OMe，-N(CH2CH3)2)会引起吸收带的红移。另一方面，9a-9g的荧光光谱显示硼酸上的吸电子基团和水杨醛上的给电子基团，导致荧光发射带增强(图2)。一般来说，配合物9a-9g显示出中等到大的斯托克斯位移(53-92nm)，量子产率范围为0.01-0.26。
表1 9a-9g的光物理性质
本发明提供一类亚氨基硼酸盐化合物，该类化合物显示出良好的光物理性质，有望开发成新型荧光探针。本发明在乙腈中无催化剂条件下α-羟基腙、水杨醛和硼酸衍生物作为起始材料，按照一锅法合成亚氨基硼酸盐化合物，所有产品均可通过过滤和洗涤快速纯化。本发明合成方法的优点包括无催化剂、反应时间短、易于后处理，以及它们能够适应广泛的底物，以及良好的产率。此外，通过简单的过滤和洗涤，可以方便地纯化产品。
实验数据：
Iminoboronate 9a.light green solid(0.21g,61％yield)；mp 249-251℃,1HNMR (600MHz,CDCl3)δ8.53(1H,s),7.76(2H,d,J7.3),7.48(1H,t,J7.4),7.44–7.39 (5H,m),7.36(1H,dd,J7.8,1.6),7.23(2H,t,J7.1),7.19(1H,t,J7.2),6.97(1H, d,J8.4),6.85(1H,t,J7.5),5.16(1H,d,J19.2),4.85(1H,d,J19.2).13C NMR(151 MHz,CDCl3)δ169.87,160.31,156.17,138.05,132.87,132.01,131.81,130.84,128.82, 127.65,127.43,126.46,120.02,119.63,116.14,63.89.11B NMR(193MHz,CDCl3)δ 4.40.HRMS(ESI):m/z[M+H]+calculated for C21H18BN2O2:341.1455,found: 341.1450.
Iminoboronate 9b.light green solid(0.20g,57％yield)；mp 265-267℃,1HNMR (600MHz,CDCl3)δ8.52(1H,s),7.76(2H,d,J7.2),7.48(1H,t,J7.4),7.44–7.39 (3H,m),7.36(1H,dd,J7.8,1.6),7.32(2H,d,J7.8),7.05(2H,d,J7.6),6.96(1H, d,J8.4),6.84(1H,t,J7.5),5.16(1H,d,J19.2),4.85(1H,d,J19.2),2.25(4H,s). 13C NMR(151MHz,CDCl3)δ169.82,160.35,156.10,137.98,136.89,132.91,131.97, 131.78,130.90,128.80,128.46,126.45,120.05,119.57,116.16,63.90,21.29.11B NMR(193MHz,CDCl3)δ4.44.HRMS(ESI):m/z[M+H]+calculated for C22H20BN2O2:355.1612,found:355.1614.
Iminoboronate 9c.light green solid(0.20g,55％yield)；mp 234-236℃,1HNMR (600MHz,CDCl3)δ8.52(1H,s),7.76(2H,d,J7.3),7.48(1H,t,J7.4),7.44–7.39 (3H,m),7.35(3H,dd,J14.1,4.8),7.07(2H,d,J8.0),6.96(1H,d,J8.4),6.84(1H, t,J7.5),5.16(1H,d,J19.2),4.86(1H,d,J19.2),2.56(2H,q,J7.6),1.17(3H,t,J 7.6).13C NMR(151MHz,CDCl3)δ169.80,160.38,156.07,143.14,137.96,132.93, 131.96,131.78,130.88,128.80,127.21,126.46,120.05,119.54,116.16,63.90,28.65, 15.30.11B NMR(193MHz,CDCl3)δ4.52.HRMS(ESI):m/z[M+H]+calculated for C23H22BN2O2:369.1768,found:369.1771.
Iminoboronate 9d.light green solid(0.25g,60％yield)；mp263-265℃,1HNMR (600MHz,CDCl3)δ8.52(1H,s),7.74(2H,d,J7.4),7.48(1H,t,J7.4),7.44(1H, t,J7.8),7.40(2H,t,J7.7),7.37(1H,d,J6.3),7.33(2H,d,J8.2),7.26(2H,d,J 8.1),6.95(1H,d,J8.4),6.86(1H,t,J7.5),5.14(1H,d,J19.3),4.78(1H,d,J19.2). 13C NMR(151MHz,CDCl3)δ169.92,160.09,156.26,138.27,132.67,132.16,131.86, 130.75,128.88,126.43,121.78,119.95,119.87,116.01,63.78.11BNMR(193MHz, CDCl3)δ4.18.HRMS(ESI):m/z[M+H]+calculated for C21H17BN2O2Br:419.0561, found:419.0566.
Iminoboronate 9e.light green solid(0.22g,58％yield)；mp 235-238℃,1HNMR (600MHz,CDCl3)δ8.61(1H,s),8.05(2H,d,J8.7),7.76(2H,d,J7.2),7.56(2H, d,J8.6),7.49(2H,dt,J8.7,4.6),7.43(3H,t,J7.5),6.98(1H,d,J8.4),6.92(1H,t, J7.5),5.18(1H,d,J19.3),4.77(1H,d,J19.4).13C NMR(151MHz,CDCl3)δ169.96, 159.81,156.58,147.73,138.61,132.41,132.38,132.02,131.66,128.96,126.44, 122.58,120.23,119.88,115.87,63.62.11B NMR(193MHz,CDCl3)δ3.66.HRMS (ESI):m/z[M+H]+calculatedfor C21H17BN3O4:386.1306,found:386.1308.
Iminoboronate 9f.light green solid(0.21g,57％yield)；mp257-259℃,1HNMR (600MHz,CDCl3)δ8.40(1H,s),7.71(2H,d,J7.3),7.44(1H,t,J7.4),7.41(1H, d,J6.7),7.37(2H,t,J7.6),7.22(3H,dd,J14.2,6.2),7.17(1H,t,J7.2),6.44–6.39 (2H,m),5.10(1H,d,J19.0),4.79(1H,d,J19.0),3.77(3H,s).13C NMR(151MHz, CDCl3)δ168.27,167.77,162.95,154.98,133.20,133.06,131.59,130.88,128.74, 127.64,127.35,126.26,109.97,109.68,102.48,63.79,55.68.11B NMR(193MHz, CDCl3)δ4.11.HRMS(ESI):m/z[M+H]+calculated for C22H20BN2O3:371.1561, found:371.1565.
Iminoboronate 9g.light green solid(0.25g,62％yield)；mp 251-253℃,1HNMR (600MHz,CDCl3)δ8.23(1H,s),7.71(2H,d,J7.2),7.45(2H,d,J6.7),7.41(1H,t,J7.3),7.36(2H,t,J7.4),7.22(2H,t,J7.2),7.16(1H,t,J7.3),7.12(1H,d,J9.0), 6.21(1H,d,J6.8),6.12(1H,s),5.07(1H,d,J18.7),4.76(1H,d,J18.7),3.39(2H, dq,J14.3,7.1),3.31(2H,dq,J14.4,7.1),1.16(6H,t,J7.1).13C NMR(151MHz, CDCl3)δ164.63,162.19,155.45,153.38,133.87,133.54,131.08,130.89,128.61, 127.48,126.95,125.99,106.47,105.72,99.37,63.53,44.99,12.68.11B NMR(193 MHz,CDCl3)δ3.68.HRMS(ESI):m/z[M+H]+calculated for C25H27BN3O2: 412.2190,found:412.2193。
Claims (10)
1.一类亚氨基硼酸盐化合物，结构如下：
其中，R’为各自独立的氢，C1-C6的烷基或C1-C6的烷氧基，卤素、N,N二烷基；
R为各自独立的氢，C1-C6的烷基或C1-C6的烷氧基，卤素、一个或多个卤素取代的甲基、硝基、羟基。
2.如权利要求1所述的化合物，其特征在于：所述C1-C6烷基是指甲基、乙基、丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、新戊基、正己基或异己基；所述C1-C6的烷氧基是指甲氧基或乙氧基；所述卤素是氟、氯、溴或碘。
3.如权利要求1所述的化合物，其特征在于：N,N二烷基是指N,N二甲基或N,N二乙基。
4.如权利要求1所述的化合物，其特征在于：R’独立的为邻位、间位或对位，可以邻位、间位和对位同时取代，也可以单独取代；R可以独立的为邻位、间位或对位，可以邻位、间位和对位同时取代，也可以单独取代。
5.如权利要求1所述的化合物，其特征在于：所述式9化合物选自9a-9g化合物：
6.如权利要求1-5任一项所述化合物的制备方法，其特征在于，合成路线如下：
7.如权利要求6所述的方法，其特征在于：反应溶剂选自四氢呋喃、甲醇、乙腈、N,N-二甲基甲酰胺、丙酮、乙酸乙酯中的一种或几种混合。
8.如权利要求6所述的方法，其特征在于：溶剂选自乙酸乙酯或乙腈。
9.如权利要求6所述的方法，其特征在于：反应温度为80℃。
10.如权利要求1-5任一项所述式9化合物作为荧光探针中的应用。
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