CN106432320B - 一种含缩醛结构的有机硫化氢供体及其制备方法 - Google Patents
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
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- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
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Abstract
本发明提供一种含缩醛结构的有机硫化氢供体及其制备方法。所述的有机硫化氢供体在特定条件下能分解释放出H2S气体。其制备方法为:以苯甲酰硅如三乙基苯甲酰硅、叔丁基二甲基苯甲酰硅或异丙基苯甲酰硅分别和三苯基硫醇、硫代苯甲酸或对甲基苯硫酚在光照作用下发生brook重排反应,可制得硅烷基和巯基保护的缩醛类化合物。该制备方法具有操作简单方便、反应时间短、副反应少等优点。
Description
技术领域
本发明涉及硫、硅化合物制备,具体涉及含缩醛结构的有机硫化氢供体及其制备方法,以及合成的有机硫化氢供在H2S生物信号分子研究中的应用。
背景技术
H2S被发现是继NO、CO之后的第三个生物信号分子以来,引起了科学家们的高度重视,我们已经知道在机体内内源性H2S的浓度是微摩尔级,甚至是毫摩尔级的,但它却起着非常重要的生理学和生物学功能。因此,开辟能在细胞内和细胞外有效应用的H2S供体对研究H2S的生理学功能及在体内的信号转导过程是非常重要的。
目前,H2S研究的主要来源有三种:一、直接用H2S气体或者H2S饱和溶液。H2S气体不好操作,易污染环境,易中毒。二、无机盐硫化钠、硫氢化钠作为H2S供体。这类供体H2S释放过快,而且H2S气体不断从溶液中挥发,溶液使用的有效时间短,有效浓度不准确。三、有机H2S供体。它们相对于H2S无机盐供体更稳定、缓释、毒副作用小。
发明内容
本发明的目的是提供一种含缩醛结构的有机硫化氢供体及其制备方法,该有机硫化氢供体为硅烷基和巯基保护的缩醛类化合物,它脱去硅烷基和巯基保护剂后生成含一个巯基和一个羟基的缩醛(巯基苯基甲醇),该化合物不稳定,会释放出H2S气体变为苯甲醛,因此可作为有机H2S供体。本发明所制备的H2S供体稳定、缓释、毒副作用小,所采用的制备方法操作简单方便、反应时间短、副反应少。
本发明提供的一种含缩醛结构的有机硫化氢供体,其结构式为:
式中:
本发明提供的一种含缩醛结构的有机硫化氢供体的制备方法,反应式为:
制备方法,包括如下步骤:
将苯甲酰硅和R'SH溶于无水的有机溶剂中,加入吡啶提供碱性,密封;用250W红外反射灯光照0.5~3h,当体系的黄色褪去,反应结束;减压旋除溶剂得粗产品,粗产品用中性氧化铝柱色谱(展开剂为正己烷)分离得产品;
所述的苯甲酰硅为三乙基苯甲酰硅、叔丁基二甲基苯甲酰硅或异丙基苯甲酰硅;
所述的R'SH为三苯基硫醇、硫代苯甲酸或对甲基苯硫酚。
所述的苯甲酰硅和R'SH的摩尔比为1:1~1.5;苯甲酰硅和吡啶的摩尔比1:0.025—0.1。
所述的苯甲酰硅和R'SH的最佳摩尔比为1:1.2;苯甲酰硅和吡啶的最佳摩尔比为1:0.05。
所述的溶剂为无水的二氯甲烷、四氢呋喃、二氧六环或乙腈。最佳溶剂为二氯甲烷,溶剂的最佳量为2.0mL(二氯甲烷)/1.0mmol(苯甲酰硅)。
所述的反应是在耐热耐压试管中密封进行;反应温度为140℃。反应完全的标准为反应体系黄色褪去。
与现有技术相比,本发明的有益效果:
本发明方法操作简单方便、不需要特殊的催化剂、反应时间短、副反应少、试管密封进行对环境污染小等,反应产率为48%~70%。
本发明制备的含缩醛结构的有机硫化氢供体,在特定的条件下,脱去巯基保护剂R’,再脱去硅烷基SiR3,可生成含一个巯基和一个羟基的缩醛(巯基苯基甲醇),这个结构不稳定,可分解释放出H2S气体。条件合适时,也可同时脱去巯基和硅烷基两个保护基,直接生成巯基苯基甲醇。如下所示:
本发明提供的由三乙基苯甲酰硅和三苯基硫醇反应生成的化合物苯甲醛三乙基硅氧基硫代三苯基缩醛(1),在二氯甲烷溶剂中,-10℃的条件下,加入等摩尔的FeCl3,搅拌,可释放H2S气体。如下式所示。
本发明提供的由三乙基苯甲酰硅和硫代苯甲酸反应生成的化合物苯甲醛三乙基硅氧基硫代苯甲酰基缩醛(2),在甲醇:磷酸缓冲溶液为8:2的溶剂中,pH为4.5的条件下,加入5倍量的半胱氨酸(Cys),室温搅拌,可释放H2S气体。如下式所示
本发明中合成的其它化合物在适当条件下也可释放H2S气体。
具体实施方式
反应条件筛选和优化:
反应原料是按照文献Organometallics 1994,13,2461-2466制备,条件筛选反应的具体反应步骤为:在耐热耐压的玻璃试管中,加入三乙基苯甲酰硅(200mg,1.09mmol),三苯基硫醇(如表1所示),微量吡啶和反应溶剂,封管,用250W反射红外灯光照,黄色褪去,停止反应,减压除去二氯甲烷,中性氧化铝柱色谱分离(展开剂为正己烷)得化合物(1)。具体用量和溶剂如表1所示.
根据表1的实验结果,得到苯甲酰硅和R'SH的最佳摩尔比1:1.2,最佳溶剂为无水二氯甲烷,苯甲酰硅和吡啶最佳摩尔比为1:0.05,溶剂的最佳量为2.0mL(二氯甲烷)/1.0mmol(苯甲酰硅)。反应体系的实际温度为140℃。
表1反应条件筛选和优化
表中所说的比例指摩尔比
实施例1:三乙基苯甲酰硅和三苯基硫醇制备苯甲醛三乙基硅氧基硫代三苯基缩醛(1)
在耐热耐压的玻璃试管中,加入三乙基苯甲酰硅(200mg,0.91mmol),三苯基硫醇(301mg,1.09mmol),35μL(4.5μmol)吡啶和1.8mL无水二氯甲烷,封管,用250W反射红外灯光照95min,黄色褪去,停止反应,减压除去二氯甲烷,中性氧化铝柱色谱分离(展开剂为正己烷)得产物249mg,产率55%。
实施例2:三乙基苯甲酰硅和硫代苯甲酸制备苯甲醛三乙基硅氧基硫代苯甲酰基缩醛(2)
在耐热耐压的玻璃试管中,加入三乙基苯甲酰硅(200mg,0.91mmol),硫代苯甲酸(150mg,1.09mmol),35μL(4.5μmol)吡啶和1.8mL无水二氯甲烷,封管,用250W反射红外灯光照120min,黄色褪去,停止反应,减压除去二氯甲烷,中性氧化铝柱色谱分离(展开剂为正己烷)得产物157mg,产率48%。
实施例3:三乙基苯甲酰硅和对甲基苯硫酚制备苯甲醛三乙基硅氧基对甲基苯硫酚基缩醛(3)
在耐热耐压的玻璃试管中,加入三乙基苯甲酰硅(200mg,0.91mmol),对甲基苯硫酚(135mg,1.09mmol),35μL(4.5μmol)吡啶和1.8mL无水二氯甲烷,封管,用250W反射红外灯光照120min,黄色褪去,停止反应,减压除去二氯甲烷,中性氧化铝柱色谱分离(展开剂为正己烷)得产物188mg,产率60%。
实施例4:叔丁基二甲基苯甲酰硅和三苯基硫醇制备苯甲醛叔丁基二甲基硅氧基硫代三苯基缩醛(4)
在耐热耐压的玻璃试管中,加入叔丁基二甲基苯甲酰硅(200mg,0.91mmol),三苯基硫醇(301mg,1.09mmol),35μL(4.5μmol)吡啶和1.8mL无水二氯甲烷,封管,用250W反射红外灯光照120min,黄色褪去,停止反应,减压除去二氯甲烷,中性氧化铝柱色谱分离(展开剂为正己烷)得产物316mg,产率70%。
实施例5:叔丁基二甲基苯甲酰硅和硫代苯甲酸制备苯甲醛叔丁基二甲基硅氧基硫代苯甲酰基缩醛(5)
在耐热耐压的玻璃试管中,加入叔丁基二甲基苯甲酰硅(200mg,0.91mmol),硫代苯甲酸(150mg,1.09mmol),35μL(4.5μmol)吡啶和1.8mL无水二氯甲烷,封管,用250W反射红外灯光照120min,黄色褪去,停止反应,减压除去二氯甲烷,中性氧化铝柱色谱分离(展开剂为正己烷)分离得产物206mg,产率63%。
实施例6:叔丁基二甲基苯甲酰硅和对甲基苯硫酚制备苯甲醛叔丁基二甲基硅氧基对甲基苯硫酚基缩醛(6)
在耐热耐压的玻璃试管中,加入叔丁基二甲基苯甲酰硅(200mg,0.91mmol),对甲基苯硫酚(135mg,1.09mmol),35μL(4.5μmol)吡啶和1.8mL无水二氯甲烷,封管,用250W反射红外灯光照150min,黄色褪去,停止反应,减压除去二氯甲烷,中性氧化铝柱色谱分离(展开剂为正己烷)得产物176mg,产率56%。
实施例7:三异丙基苯甲酰硅和三苯基硫醇制备苯甲醛三异丙基硅氧基硫代三苯基缩醛(7)
在耐热耐压的玻璃试管中,加入三异丙基苯甲酰(200mg,0.76mmol),三苯基硫醇(252mg,0.91mmol),30μL(3.8μmol)吡啶和1.5mL无水二氯甲烷,封管,用250W反射红外灯光照180min,黄色褪去,停止反应,减压除去二氯甲烷,中性氧化铝柱色谱分离(展开剂为正己烷)得产物213mg,产率52%。
实施例8:三异丙基苯甲酰硅和硫代苯甲酸制备苯甲醛三异丙基硅氧基硫代苯甲酰基缩醛(8)
在耐热耐压的玻璃试管中,加入三异丙基苯甲酰(200mg,0.76mmol),硫代苯甲酸(126mg,0.91mmol),30μL(3.8μmol)吡啶和1.5mL无水二氯甲烷,封管,用250W反射红外灯光照180min,黄色褪去,停止反应,减压除去二氯甲烷,中性氧化铝柱色谱分离(展开剂为正己烷)得产物171mg,产率56%。
实施例1-8得到的产物的分子结构、1HNMR、13CNMR和MS数据见表2。
表2缩醛类化合物的分子结构、1HNMR、13CNMR和MS数据
Claims (7)
1.一种含缩醛结构的有机硫化氢供体,其结构式为:
式中:
2.如权利要求1所述的含缩醛结构的有机硫化氢供体的制备方法,其特征在于,包括如下步骤:
将苯甲酰硅和R'SH溶于无水的有机溶剂中,加入吡啶提供碱性,密封;用250W红外反射灯光照0.5~3h,当体系的黄色褪去,反应结束;减压旋除溶剂得粗产品,粗产品用中性氧化铝柱色谱分离得产品;
所述的苯甲酰硅为三乙基苯甲酰硅;
所述的R'SH为三苯基硫醇或硫代苯甲酸。
3.如权利要求2所述的有机硫化氢供体的制备方法,其特征在于,所述的苯甲酰硅和R'SH的摩尔比为1:1~1.5;苯甲酰硅和吡啶的摩尔比1:0.025—0.1。
4.如权利要求3所述的有机硫化氢供体的制备方法,其特征在于,所述的苯甲酰硅和R'SH的最佳摩尔比为1:1.2;苯甲酰硅和吡啶的最佳摩尔比为1:0.05。
5.如权利要求2所述的有机硫化氢供体的制备方法,其特征在于,所述的溶剂为无水的二氯甲烷、四氢呋喃、二氧六环或乙腈。
6.如权利要求5所述的有机硫化氢供体的制备方法,其特征在于,所述的溶剂为无水二氯甲烷;溶剂的加入量为:每1.0mmol苯甲酰硅加入2.0mL二氯甲烷。
7.如权利要求2所述的有机硫化氢供体的制备方法,其特征在于,所述的反应是在耐热耐压试管中密封进行;反应温度为140℃。
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