CN109422732B - 一种1,2,4,5-四取代咪唑的制备方法 - Google Patents

一种1,2,4,5-四取代咪唑的制备方法 Download PDF

Info

Publication number
CN109422732B
CN109422732B CN201710729016.XA CN201710729016A CN109422732B CN 109422732 B CN109422732 B CN 109422732B CN 201710729016 A CN201710729016 A CN 201710729016A CN 109422732 B CN109422732 B CN 109422732B
Authority
CN
China
Prior art keywords
catalyst
znin
preparation
substrate
benzylamine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710729016.XA
Other languages
English (en)
Other versions
CN109422732A (zh
Inventor
王峰
王敏
李利花
罗能超
张晓辰
刘美江
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN201710729016.XA priority Critical patent/CN109422732B/zh
Publication of CN109422732A publication Critical patent/CN109422732A/zh
Application granted granted Critical
Publication of CN109422732B publication Critical patent/CN109422732B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/60—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by oxygen or sulfur atoms, attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

本发明涉及到一种1,2,4,5‑四取代咪唑的制备方法。该方法以卞胺为底物，在可见光光照条件下，Mo掺杂ZnIn2S4(Mo‑ZnIn2S4)作为光催化剂，卞胺发生光催化的环化，得到1,2,4,5‑四取代咪唑化合物。本发明提供了一种新的取代咪唑化合物的制备方法，条件温和，产品收率高，具有很好的应用前景。

Description

一种1,2,4,5-四取代咪唑的制备方法
技术领域
本发明涉及到一种1,2,4,5-四取代咪唑的制备方法。
背景技术
咪唑是一类重要的化工原料，是精细化学品和大宗工业化学品合成的重要中间体，广泛应用于制药、香料、农业化学品、聚合物等。传统的取代咪唑的合成方法，采用醛、酮和含氮化合物，或者采用亚胺和酰氯等多种原料为底物，通过缩合反应生成。所采用原料复杂，反应条件苛刻。本发明采用卞胺作为单一原料，在光照条件下，室温下就可以发生环化，生成1,2,4,5-四取代咪唑化合物。本方法所得取代咪唑的收率高，产物和催化剂易分离，条件温和，后处理简单；催化剂易于重复使用，具有很好的应用前景。
发明内容
本发明提供一种1,2,4,5-四取代咪唑的制备方法。该方法以卞胺及其衍生物为底物，在可见光光照条件下，在催化剂为ZnIn2S4催化剂作用，卞胺发生光催化的环化，得到取代的咪唑化合物。
所述三取代的咪唑化合物结构如下：
Figure BDA0001386667660000011
其中R为苯基及苯环取代的衍生物，或者呋喃和噻吩.所述苯环取代的衍生物，取代基为氟、氯、溴、甲基、甲氧基等中的一种或者二种以上，取代基个数为1-5个。
所述卞胺及其衍生物中衍生物指的是苯环取代的衍生物，取代基为氟、氯、溴、甲基、甲氧基等中的一种或者一种以上，取代基个数为1-5个；2-胺甲基呋喃和2-胺甲基噻吩。
在可见光激发下，底物分子本身不会吸光，需要采用光催化剂，本发明发现ZnIn2S4可以实现在可见光作用下，三分子卞胺发生环化，生成1,2,4,5-四取代咪唑化合物。
所用Mo-ZnIn2S4催化剂与底物的质量比为：0.1-20wt％。Mo的掺杂量影响到催化剂的催化性能，本发明采用的钼掺杂的硫化铟锌Mo-ZnIn2S4,Mo与Zn的摩尔比1-20：100。
可见光的波长为400-500nm。
为了使底物与催化剂充分接触，特别是一些胺类化合物室温下是固体，需要加入溶剂使其溶解，所用溶剂为乙腈、甲苯、四氢呋喃、乙醇中一种或者一种以上。
本发明反应操作过程如下：将催化剂Mo-ZnIn2S4和卞胺加入到石英玻璃光中，再加入适量溶剂，密闭反应釜，通过氩气置换关内气体，用玻璃塞盖住口。在9.6W 455nm，LED光反应器下反应一定时间后，冷却，离心分离催化剂，催化剂用乙醇和丙酮洗涤，80℃干燥后重复使用。
产品的定性采用气相色谱-质谱分析，并和标准样品的保留时间进行比对；定量用内标法气相色谱分析。
本发明提供了一种新的1,2,4,5-四取代咪唑化合物的制备方法，条件温和，产品收率高，具有很好的应用前景。
本发明具有如下特点：催化剂体系简单、高效，副产物少，催化剂用量少，催化剂与产物易分离，催化剂可循环使用。
附图说明
图1实施例1中合成1,2,4,5-四取代咪唑核磁图。
具体实施方式
下面通过具体实施例对本发明进行说明，但本发明实施不局限于这些实施例：
实施例1-8：将0.1g卞胺，一定量的Mo与Zn的摩尔比为4％的Mo-ZnIn2S4，2mL溶剂加入到5mL石英反应管中，通入氩气置换，密闭反应管，磁子搅拌，在9.6W455nm，LED光反应器下反应一定时间后，离心分离催化剂。所得样品定性分析采用气相色谱-质谱联用技术，定量分析由气相色谱实现，结果见表1。
表1卞胺光催化环化制备的1,2,4,5-四取代咪唑化合物
Figure BDA0001386667660000021
分析表1中结果可知，咪唑收率随着催化剂用量增加和反应时间延长而增加。在不同反应溶剂中乙腈、甲苯、四氢呋喃和乙醇等溶剂中，都有比较好的效果。
实施例9-13：将0.1g卞胺，0.01g不同Mo掺杂量的Mo-ZnIn2S4，2mL溶剂加入到5mL石英反应管中，通入氩气置换，密闭反应管，磁子搅拌，在9.6W 455nm，LED光反应器下反应一定时间后，离心分离催化剂。所得样品定性分析采用气相色谱-质谱联用技术，定量分析由气相色谱实现，结果见表2。
表2卞胺光催化环化制备的1,2,4,5-四取代咪唑化合物
Figure BDA0001386667660000031
分析表2中结果可知，随着Mo掺杂量的增加，1,2,4,5-四取代咪唑化合物收率逐渐增加，当掺杂量超过5％之后，1,2,4,5-四取代咪唑化合物收率逐渐增加有所下降。因此，Mo掺杂量需要达到一个适中的量，才会得到好的催化效果
实施例14-22，将0.1g胺底物，0.01g Mo与Zn的摩尔比为5％的Mo-ZnIn2S4，2mL乙腈加入到5mL石英反应管中，通入氩气置换，密闭反应管，磁子搅拌，在9.6W 455nm，LED光反应器下反应24小时后，离心分离催化剂。所得样品定性分析采用气相色谱-质谱联用技术，定量分析由气相色谱实现，结果见表3。
表3不同胺类底物光催化环化制备1,2,4,5-四取代咪唑化合物
Figure BDA0001386667660000032
Figure BDA0001386667660000033
Figure BDA0001386667660000041
分析表3中结果可知，不同基团取代的卞胺，2-胺甲基呋喃和2-胺甲基噻吩都可以得到1,2,4,5-四取代咪唑化合物。实例20所示，位组大的卞胺，四取代咪唑化合物收率不高。

Claims (6)

1.一种1,2,4,5-四取代咪唑的制备方法，其特征在于：在可见光光照条件下，在催化剂作用下，以R-CH2-NH2作为底物，发生光催化的环化反应，得到如下式所示的1,2,4,5-四取代的咪唑化合物
Figure 502525DEST_PATH_IMAGE001
；
所述催化剂为钼掺杂的硫化铟锌Mo-ZnIn2S4；
所述R为呋喃、噻吩或任意被取代的苯基；
取代基为氟、氯、溴、甲基、甲氧基中的一种或者二种以上，取代基个数为1-5个；
所用催化剂与底物的质量比为：0.1- 20 wt%； 反应时间为2-48 h；
钼掺杂的硫化铟锌Mo-ZnIn2S4，Mo与Zn的摩尔比1-20：100。
2.根据权利要求1所述的方法，其特征在于：
所述R为呋喃和噻吩时，2位碳与亚甲基相连，底物为：2-胺甲基呋喃和2-胺甲基噻吩。
3.根据权利要求1所述的方法，其特征在于：反应时间为12-24 h。
4.根据权利要求1所述的方法，其特征在于：钼掺杂的硫化铟锌Mo-ZnIn2S4, Mo与Zn的摩尔比3-10:100。
5.根据权利要求1所述的方法，其特征在于：采用溶剂为乙腈、甲苯、四氢呋喃、乙醇中一种或者二种以上。
6.根据权利要求1所述的方法，其特征在于：可见光的波长为 400-500 nm。
CN201710729016.XA 2017-08-23 2017-08-23 一种1,2,4,5-四取代咪唑的制备方法 Active CN109422732B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710729016.XA CN109422732B (zh) 2017-08-23 2017-08-23 一种1,2,4,5-四取代咪唑的制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710729016.XA CN109422732B (zh) 2017-08-23 2017-08-23 一种1,2,4,5-四取代咪唑的制备方法

Publications (2)

Publication Number Publication Date
CN109422732A CN109422732A (zh) 2019-03-05
CN109422732B true CN109422732B (zh) 2021-02-09

Family

ID=65498281

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710729016.XA Active CN109422732B (zh) 2017-08-23 2017-08-23 一种1,2,4,5-四取代咪唑的制备方法

Country Status (1)

Country Link
CN (1) CN109422732B (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112264049B (zh) * 2020-10-14 2023-08-25 盐城工学院 一种用于光催化固氮合成氨的Mo或Fe掺杂Zn1-xIn2S4催化剂的制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (2)

* Cited by examiner, † Cited by third party
Title
Copper-Catalyzed Aerobic Oxidation of Amines to Imines under Neat Conditions with Low Catalyst Loading;Rajendra D.等;《Adv. Synth. Catal.》;20110630;第353卷;第1695-1700页 *
可见光诱导的胺氧化反应研究;宣俊;《华中师范大学博士学位论文》;20151231;全文 *

Also Published As

Publication number Publication date
CN109422732A (zh) 2019-03-05

Similar Documents

Publication Publication Date Title
Jin et al. A clean one-pot synthesis of tetrahydrobenzo [b] pyran derivatives catalyzed by hexadecyltrimethyl ammonium bromide in aqueous media
Sakai et al. Indium-catalyzed direct conversion of lactones into thiolactones and selenolactones in the presence of elemental sulfur and selenium
CN109422732B (zh) 一种1,2,4,5-四取代咪唑的制备方法
Kassaee et al. ZnO nanoparticles as an efficient catalyst for the one-pot synthesis of α-amino phosphonates
Capperucci et al. Organoselenosilane-mediated selective mild access to selenolesters, selenoanhydrides and diacyl diselenides
CN109422692B (zh) 一种2,4,5-三取代咪唑化合物的制备方法
Panduranga et al. Alternative protocol for the synthesis of symmetrical dibenzyl diselenides and disulfides
CN111018879A (zh) 一种噻吩并[3,2-b]吲哚衍生物及其合成方法
CN111960975B (zh) 一种烯丙基硫醚类化合物及其制备方法
CN108689892A (zh) 3-磺酰化-二氢茚酮类化合物及其制备方法
CN111362795B (zh) 一类取代丁酸酯类衍生物的制备方法
CN106518634A (zh) 一种光催化α‑二酮化合物的制备方法
Bonanni et al. Novel L-tartaric acid derived pyrrolidinium cations for the synthesis of chiral ionic liquids
CN106431983B (zh) 一种2-苄氧基苯甲腈类化合物及其制备方法
CN111704591A (zh) 一种铜催化硫代萘并噻唑酮类化合物的合成方法
Capperucci et al. Stereoselective functionalization of dithiolanes and dithianes: the first example of an axial trapping
Srihari et al. A facile nucleophilic displacement of Baylis-Hillman acetates with ammonium thiocyanate
CN112159344B (zh) 一种1,3-二甲基-3-羟甲基吲哚啉-2-酮化合物的合成方法
CN107501024A (zh) 一种1,2‑二碘代烯烃类化合物的合成方法
CN114524751B (zh) 一类芳基腈类化合物及其制备方法
CN112125843B (zh) 一种3-羟甲基-4-苯基-3,4-二氢喹啉酮化合物的制备方法
CN1575272A (zh) 制备4－亚硝基取代的芳香胺的方法
CN109265311B (zh) 一种苯基芴衍生物及其制备方法与应用
CN111909113A (zh) 一种无催化剂和无添加剂条件下2-取代苯并噻唑类化合物的合成方法
CN110256368B (zh) 一种脒类化合物与氮杂环丙烷化合物环加成的方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant