CN109134368B - 一种由1,2,3,4-四氢异喹啉半脱氢氧化合成3,4-二氢异喹啉的方法 - Google Patents
一种由1,2,3,4-四氢异喹啉半脱氢氧化合成3,4-二氢异喹啉的方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
- C07D217/02—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with only hydrogen atoms or radicals containing only carbon and hydrogen atoms, directly attached to carbon atoms of the nitrogen-containing ring; Alkylene-bis-isoquinolines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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Abstract
本发明公开了一种由1,2,3,4‑四氢异喹啉半脱氢氧化合成3,4‑二氢异喹啉的方法,属于有机化学和光催化技术领域。该方法以MoS2/ZnIn2S4为光催化剂,在可见光条件下,在N2气氛中实现1,2,3,4‑四氢异喹啉的半脱氢氧化,产物为3,4‑二氢异喹啉,具有高的转化率和选择性。同时该方法简便易行,有利于大规模的工业推广。
Description
技术领域
本发明属于有机化学及光催化领域,具体涉及到一种由1,2,3,4-四氢异喹啉半脱氢氧化合成3,4-二氢异喹啉的方法。
背景技术
1,2,3,4-四氢异喹啉是一类自然界中分布十分广泛的生物碱,其脱氢产物异喹啉类化合物是一类重要的化工中间体,广泛用于有机导电体、染料、感光色素、杀虫剂、生物碱、医药及杀菌剂、橡胶硫化促进剂等化合物的合成中,其中,半脱氢产物3,4-二氢异喹啉是合成许多吗啡喃化合物的重要中间体,吗啡喃化合物在医药领域中被广泛应用于疼痛缓解。因此,在有机化学的合成研究中,发展一种高效合成3,4-二氢异喹啉化合物的方法具有十分重要的意义。目前已报道的通过1,2,3,4-四氢异喹啉直接半脱氢合成3,4-二氢异喹啉的方法可以分为两类:一类是在有氧化剂的参与下氧化脱氢,利用氧气或其他氧化剂合成3,4-二氢异喹啉,但由于氧化剂的存在使得在生成3,4-二氢异喹啉后往往伴随进一步的脱氢,产物的选择性较差;另一类是在无氧化剂条件下,利用Ir、Ru等贵金属配合物催化脱氢,但由于催化剂成本高且反应温度较高使得这种方法的应用也受到了局限。因此寻找一种温和、简单、高效的催化体系是十分有必要的。
近年来,光催化有机反应因其绿色、高效、温和等特点在有机合成领域得到了广泛应用,光催化1,2,3,4-四氢异喹啉部分脱氢合成3,4-二氢异喹啉类化合物也具有很大的应用前景。但目前只局限在1,2,3,4-四氢异喹啉脱氢生成异喹啉,部分脱氢生成3,4-二氢异喹啉的相关报道很少,而且,在1,2,3,4-四氢异喹啉的光催化脱氢过程中使用的光催化剂一般是在可见光下有强吸收的贵金属Ru、Ir结合吡啶类似物的配体形成的络合物,但由于贵金属及其配体的合成成本较高,限制了大规模的生产。
半导体光催化剂因其价廉易得,结构稳定,光吸收性能好等优势已在很多光催化体系中有着非常优异的表现。近年来,ZnIn2S4因具有合适的禁带宽度,使其在可见光区具有很强的光吸收性能,而且其导带价带的位置也为实现多种氧化还原反应提供了可能。而MoS2是一个优异的产氢助催化剂,其导带位置位于-0.5~-0.9eV vs NHE之间,比六方相ZnIn2S4更低,因此理论上光生电子可以从ZnIn2S4迁移到MoS2,可以有效地降低光生电子和光生空穴的复合,从而可以使催化剂具有更高的催化活性。
发明内容
本发明的目的在于提供一种由1,2,3,4-四氢异喹啉半脱氢氧化合成3,4-二氢异喹啉的方法,以MoS2/ZnIn2S4为催化剂,在N2中实现1,2,3,4-四氢异喹啉部分脱氢为3,4-二氢异喹啉,具有高的转化率和选择性,方法简便易行,有利于大规模的工业推广。
为实现上述目的,本发明采用如下技术方案:
以MoS2/ZnIn2S4为光催化剂,在可见光条件下,在N2气氛中实现1,2,3,4-四氢异喹啉的半脱氢氧化。具体步骤为:称取10mg MoS2/ZnIn2S4光催化剂置于10ml的schlenk管中并抽真空,然后用高纯N2反复洗气以除掉schlenk管中的氧气。将0.1mmol1,2,3,4-四氢异喹啉溶解在2mL的反应溶剂中,然后通入高纯N2 5分钟来除掉溶解在溶液中的氧气,随后取2ml上述溶液转移至装有光催化剂的schlenk管中。最后将其放入多通道光催化平行反应装置(PCX50B Discover,5W, LED发射光的波长集中在450nm)中。反应结束后,气相产物通过TCD检测器定量检测,液相产物先用多孔滤头过滤掉固体催化剂,然后用乙酸乙酯萃取三次,最后用GC-MS定性检测,用配有FID检测器的气相色谱定量检测。
所述光催化剂MoS2/ZnIn2S4的制备方法,包括以下步骤:
(1)[(NH4)2MoS4]的制备:将7.5g (NH4)6Mo7O24•4H2O加入到50ml的浓氨水中,搅拌至溶解,然后再加入50ml质量分数为20%的硫化铵溶液,维持温度80℃ 1小时后将反应体系冷却至0℃,经水和乙醇洗涤、烘干后得到化合物[(NH4)2MoS4];
(2)MoS2/ZnIn2S4的制备:将200mg ZnIn2S4固体粉末和一定量的[(NH4)2MoS4]加入干燥的schlenk管中并用N2洗气三次,再加入 3ml去除过氧气的甲醇溶液,然后用300W的氙灯在可见光下光照3h,经洗涤、烘干后得到暗黄色的固体粉末MoS2/ZnIn2S4,其中MoS2的负载量为1.0 wt%。
本发明的显著优点在于:
(1)本发明在温和的条件下实现了1,2,3,4-四氢异喹啉的半脱氢氧化为3,4-二氢异喹啉,选择性高。
(2)本发明所用的光催化剂的制备方法简单易行,价格低廉且没有金属残留,有利于大规模的工业生产,具有很高的实用价值和应用前景。
附图说明
图1为MoS2/ZnIn2S4催化下1,2,3,4-四氢异喹啉和三种产物的量随时间的变化图。
具体实施方式
半导体复合催化剂MoS2/ZnIn2S4催化1,2,3,4-四氢异喹啉半脱氢氧化生成3,4-二氢异喹啉的活性测试在充满N2的密闭反应体系中进行,反应温度为室温。具体步骤为:称取10mg MoS2/ZnIn2S4光催化剂置于10ml的schlenk管中并抽真空,然后用高纯N2反复洗气以除掉schlenk管中的氧气。将0.1mmol1,2,3,4-四氢异喹啉溶解在2mL的反应溶剂中,然后通入高纯N2 5分钟来除掉溶解在溶液中的氧气,随后取2ml上述溶液转移至装有光催化剂的schlenk管中。最后将其放入多通道光催化平行反应装置(PCX50B Discover,5W, LED发射光的波长集中在450nm)中光照12h。反应结束后,气相产物通过TCD检测器定量检测,液相产物先用多孔滤头过滤掉固体催化剂,然后用乙酸乙酯萃取三次,最后用GC-MS定性检测,用配有FID检测器的气相色谱定量检测。
MoS2/ZnIn2S4光催化剂的具体制备步骤如下:
(1)[(NH4)2MoS4]的制备:将7.5g (NH4)6Mo7O24•4H2O加入到50ml的浓氨水中,搅拌至溶解,然后再加入50ml质量分数为20%的硫化铵溶液,维持温度80℃ 1小时后将反应体系冷却至0℃,经水和乙醇洗涤、烘干后得到化合物[(NH4)2MoS4];
(2)MoS2/ZnIn2S4的制备:将200mg ZnIn2S4固体粉末和[(NH4)2MoS4]加入干燥的schlenk管中并用N2洗气三次,再加入 3ml去除过氧气的甲醇溶液,然后用300W的氙灯在可见光下光照3h,经洗涤、烘干后得到暗黄色的固体粉末MoS2/ZnIn2S4,其中MoS2的负载量为1.0 wt%。
实施例1
以1,2,3,4-四氢异喹啉为底物,MoS2/ZnIn2S4为光催化剂,在N2气氛下,以乙腈(CH3CN)、水(H2O)、乙腈与水的混合溶液、DMSO与水的混合溶液和EtOH与水的混合溶液为溶剂,可见光下光照12h。反应结果如下表所示,其中当乙腈与水的体积比为2:1时,转化率和选择性整体高于其它溶剂。
表1反应溶剂对MoS2/ZnIn2S4光催化1,2,3,4-四氢异喹啉半脱氢性能的影响
注:表1中溶剂比例为体积比。
实施例2
以1,2,3,4-四氢异喹啉为底物,MoS2/ZnIn2S4为光催化剂,在N2气氛下,以乙腈与水的体积比为2:1的混合溶液作溶剂,做了不同产物随时间的变化趋势图。反应结果如图1所示,由图1可知,随时间的增加,底物1,2,3,4-四氢异喹啉的转化率不断增加,反应12h后转化率可达94%,主产物3.4-二氢异喹啉的产率随反应时间的增加缓慢降低,反应12h后产率达90%,而副产物异喹啉的产率随着反应时间的增加缓慢增加,反应12h后产率达10%,说明随时间的延长,有少量的3,4-二氢异喹啉继续脱氢生成异喹啉。该结果也表明,催化剂MoS2/ZnIn2S4对1,2,3,4-四氢异喹啉部分脱氢生成3,4-二氢异喹啉具有很好的选择性。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (6)
1.一种由1,2,3,4-四氢异喹啉半脱氢氧化合成3,4-二氢异喹啉的方法,其特征在于:以MoS2/ZnIn2S4为光催化剂,其中MoS2的负载量为1.0 wt%,在可见光条件下,在N2气氛中实现1,2,3,4-四氢异喹啉的半脱氢氧化合成3,4-二氢异喹啉。
2.根据权利要求1所述的方法,其特征在于:包括以下步骤:
1)称取10mg MoS2/ZnIn2S4光催化剂置于10ml的schlenk管中并抽真空,然后用高纯N2反复洗气以除掉schlenk管中的氧气;
2)将0.1mmol1,2,3,4-四氢异喹啉溶解在2mL的反应溶剂中,然后通入高纯N2 5分钟除掉溶解在溶液中的氧气,随后取2ml上述溶液转移至装有光催化剂的schlenk管中,将反应体系在可见光下光照12h。
3.根据权利要求2所述的方法,其特征在于:步骤2)中的反应溶剂为乙腈、水、乙腈与水的混合溶液、DMSO与水的混合溶液、乙醇与水的混合溶液中的一种。
4.根据权利要求1或2所述的方法,其特征在于:所述的光催化剂MoS2/ZnIn2S4,是一种以ZnIn2S4作为载体,以负载在ZnIn2S4上的MoS2作为助催化剂的半导体复合光催化剂。
5.根据权利要求4所述的方法,其特征在于:所述光催化剂MoS2/ZnIn2S4的制备方法包括:采用水热法合成ZnIn2S4,并通过光还原法将[(NH4)2MoS4]作为MoS2的前驱体负载在ZnIn2S4表面,合成半导体复合光催化剂MoS2/ZnIn2S4。
6.根据权利要求5所述的方法,其特征在于:所述光催化剂MoS2/ZnIn2S4的制备方法,包括如下步骤:
(1)[(NH4)2MoS4]的制备:将7.5g (NH4)6Mo7O24•4H2O加入到50ml的浓氨水中,搅拌至溶解,然后再加入50ml质量分数为20%的硫化铵溶液,维持温度80℃ 1小时后将反应体系冷却至0℃,经水和乙醇洗涤、烘干后得到化合物[(NH4)2MoS4];
(2)MoS2/ZnIn2S4的制备:将200mg ZnIn2S4固体粉末和[(NH4)2MoS4]加入干燥的schlenk管中并用N2洗气三次,再加入 3ml去除过氧气的甲醇溶液,然后用300W的氙灯在可见光下光照3h,经洗涤、烘干后得到暗黄色的固体粉末MoS2/ZnIn2S4,其中MoS2的负载量为1.0wt%。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1988000586A1 (en) * | 1986-07-18 | 1988-01-28 | Chinoin Gyógyszer és Vegyészeti Termékek Gyára Rt. | Process for the preparation of 3,4-dihydroisoquinoline |
CN103071513A (zh) * | 2013-02-27 | 2013-05-01 | 福州大学 | 一种产氢光催化剂MoS2/ZnIn2S4及其制备方法 |
CN103331175A (zh) * | 2013-07-10 | 2013-10-02 | 黑龙江大学 | 一种MoS2/ZnIn2S4纳米片复合材料的制备方法 |
CN103908971A (zh) * | 2014-04-16 | 2014-07-09 | 福州大学 | 一种用于选择性催化氧化偶联胺生成亚胺的光催化剂 |
-
2018
- 2018-09-14 CN CN201811071880.6A patent/CN109134368B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1988000586A1 (en) * | 1986-07-18 | 1988-01-28 | Chinoin Gyógyszer és Vegyészeti Termékek Gyára Rt. | Process for the preparation of 3,4-dihydroisoquinoline |
CN103071513A (zh) * | 2013-02-27 | 2013-05-01 | 福州大学 | 一种产氢光催化剂MoS2/ZnIn2S4及其制备方法 |
CN103331175A (zh) * | 2013-07-10 | 2013-10-02 | 黑龙江大学 | 一种MoS2/ZnIn2S4纳米片复合材料的制备方法 |
CN103908971A (zh) * | 2014-04-16 | 2014-07-09 | 福州大学 | 一种用于选择性催化氧化偶联胺生成亚胺的光催化剂 |
Non-Patent Citations (3)
Title |
---|
Direct evidence of charge separation in a metal-organic framework: efficient and selective photocatalytic oxidative coupling of amines via charge and energy transfer;Caiyun Xu et al.;《Chem.Sci.》;20180220;第9卷(第12期);第3152-3158页 * |
Noble metal Free MoS2/ZnIn2S4 nanocomposite for acceptorless photocatalytic semi-dehydrogenation of 1,2,3,4-tetrahydroisoquinoline to produce 3,4-dihydroisoquinoline;Mingming Hao et al.;《Applied Catalysis B: Environmental》;20190404;第252卷;第18-23页 * |
ZnIn2S4 : A Photocatalyst for the Selective Aerobic Oxidation of Amines to Imines under Visible Light;Lin Ye et al.;《ChemCatChem》;20141231;第6卷;第2540-2543页 * |
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