CN116478026A - 一种2-取代环庚三烯酮类化合物的合成方法 - Google Patents

一种2-取代环庚三烯酮类化合物的合成方法 Download PDF

Info

Publication number
CN116478026A
CN116478026A CN202310465066.7A CN202310465066A CN116478026A CN 116478026 A CN116478026 A CN 116478026A CN 202310465066 A CN202310465066 A CN 202310465066A CN 116478026 A CN116478026 A CN 116478026A
Authority
CN
China
Prior art keywords
substituted
compound
formula
cycloheptatrienone
mmol
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.)
Pending
Application number
CN202310465066.7A
Other languages
English (en)
Inventor
田仕凯
王燕
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.)
University of Science and Technology of China USTC
Original Assignee
University of Science and Technology of China USTC
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 University of Science and Technology of China USTC filed Critical University of Science and Technology of China USTC
Priority to CN202310465066.7A priority Critical patent/CN116478026A/zh
Publication of CN116478026A publication Critical patent/CN116478026A/zh
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/18—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D211/30—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by doubly bound oxygen or sulfur atoms or by two oxygen or sulfur atoms singly bound to the same carbon atom
    • C07D211/32—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by doubly bound oxygen or sulfur atoms or by two oxygen or sulfur atoms singly bound to the same carbon atom by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C07D307/80—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D309/06—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
    • C07D317/54—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
    • C07C2603/24—Anthracenes; Hydrogenated anthracenes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明属于有机合成化学领域，具体涉及一种2‑取代环庚三烯酮类化合物的合成方法，包括以下步骤：在碱性试剂存在下，将式I化合物与式II化合物在溶剂中加热反应，得到式III结构的2‑取代环庚三烯酮类化合物。本发明提供的合成方法以托品酮季铵盐(式I)和醛类化合物(式II)为原料，在碱性试剂的存在下，仅通过加热即可进行反应而生成2‑取代环庚三烯酮类化合物(式III)。本发明提供的合成方法具有原料廉价易得、操作简便、无需惰性气体保护、后处理简单、官能团兼容性好、产率高、位点选择性高的优点，且该方法放大至克级，产率依然可以保持，容易产业化。

Description

一种2-取代环庚三烯酮类化合物的合成方法
技术领域
本发明属于有机合成化学领域，具体涉及一种2-取代环庚三烯酮类化合物的合成方法。
背景技术
环庚三烯酮类化合物属于七元芳香环家族，其骨架存在于多种天然产物中，其中一些具有抗菌、抗真菌、抗癌和抗病毒活性，用作急性痛风发作和家族性地中海热的单一疗法。因此，如何高效制备含有环庚三烯酮骨架的化合物具有很高的科学意义和应用价值。
构建环庚三烯酮骨架的已知方法包括含离去基团的托品酮季铵盐衍生物的消除反应、七元碳环的氧化反应、环合反应、扩环反应以及环加成反应，存在反应物和试剂难以制备、底物范围小、位点选择性差、产率低等问题。其中，托品酮季铵盐含有β-氨基酮结构单元和七元碳环骨架，其桥环张力可以促进C(sp3)–N键在较为温和的条件下断裂。上世纪五十年代，Lornitzo、Chapman等人经过多步反应制备了含离去基团的托品酮季铵盐衍生物，将这种原料在碱溶液中加热，经过串联消除反应，得到环庚三烯酮或者4-取代环庚三烯酮。这些反应并不适用于2-取代环庚三烯酮类化合物的制备。
发明内容
有鉴于此，本发明的目的在于提供一种2-取代环庚三烯酮类化合物的合成方法，本发明提供的合成方法原料廉价易得，操作简便，产率高，同时可以放大反应，具有很好的工业应用前景。
本发明提供了一种2-取代环庚三烯酮类化合物的合成方法，包括以下步骤：
在碱性试剂存在下，将式I化合物与式II化合物在溶剂中加热反应，得到式III结构的2-取代环庚三烯酮类化合物；
其中，R1和R2独立的选择甲基、正丁基、烯丙基或苄基；X-为负离子；R为芳基或烷基。
优选的，所述R1和R2均为甲基。
优选的，所述芳基为苯基、取代苯基、萘基、取代萘基、蒽基、取代蒽基、芳杂环基、取代芳杂环基、苯并芳杂环基或取代苯并芳杂环基；所述烷基为链状烷基或环状烷基。
优选的，所述芳杂环基为吡啶基、呋喃基、噻吩基或吡咯基；所述苯并芳杂环基为喹啉基、苯并呋喃基、苯并噻吩基、咔唑基或吲哚基。
优选的，所述负离子为溴负离子、碘负离子或三氟甲磺酸根负离子。
优选的，所述碱性试剂为有机碱和/或无机碱。
优选的，所述式I化合物、式II化合物和碱性试剂的摩尔比为(1～1.2):1:(0.2～0.6)。
优选的，所述加热反应的温度为80～120℃；所述加热反应的时间为6～15h。
优选的，所述溶剂为醇类溶剂。
优选的，所述合成方法还包括：所述加热反应结束后，对得到的反应产物进行除溶剂和纯化。
与现有技术相比，本发明提供了一种2-取代环庚三烯酮类化合物的合成方法。本发明提供的合成方法包括以下步骤：在碱性试剂存在下，将式I化合物与式II化合物在溶剂中加热反应，得到式III结构的2-取代环庚三烯酮类化合物；其中，R1和R2独立的选择甲基、正丁基、烯丙基或苄基；X-为负离子；R为芳基或烷基。本发明提供的合成方法以托品酮季铵盐(式I)和醛类化合物(式II)为原料，在碱性试剂的存在下，仅通过加热即可进行反应而生成2-取代环庚三烯酮类化合物(式III)。本发明提供的合成方法具有原料廉价易得、操作简便、无需惰性气体保护、后处理简单、官能团兼容性好、产率高、位点选择性高的优点，且该方法放大至克级，产率依然可以保持，容易产业化。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据提供的附图获得其他的附图。
图1为实施例1所得产物的氢谱图；
图2为实施例1所得产物的碳谱图；
图3为实施例2所得产物的氢谱图；
图4为实施例2所得产物的碳谱图；
图5为实施例3所得产物的氢谱图；
图6为实施例3所得产物的碳谱图；
图7为实施例4所得产物的氢谱图；
图8为实施例4所得产物的碳谱图；
图9为实施例6所得产物的氢谱图；
图10为实施例6所得产物的碳谱图；
图11为实施例8所得产物的氢谱图；
图12为实施例8所得产物的碳谱图；
图13为实施例9所得产物的氢谱图；
图14为实施例9所得产物的碳谱图；
图15为实施例10所得产物的氢谱图；
图16为实施例10所得产物的碳谱图；
图17为实施例11所得产物的氢谱图；
图18为实施例11所得产物的碳谱图；
图19为实施例13所得产物的氢谱图；
图20为实施例13所得产物的碳谱图；
图21为实施例14所得产物的氢谱图；
图22为实施例14所得产物的碳谱图；
图23为实施例17所得产物的氢谱图；
图24为实施例17所得产物的碳谱图；
图25为实施例18所得产物的氢谱图；
图26为实施例18所得产物的碳谱图。
具体实施方式
下面对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明提供了一种2-取代环庚三烯酮类化合物的合成方法，包括以下步骤：在碱性试剂存在下，将式I化合物与式II化合物在溶剂中加热反应，得到式III结构的2-取代环庚三烯酮类化合物，具体反应式如下：
在本发明提供的合成方法中，所述式I化合物为托品酮季铵盐，其R1和R2独立的选择甲基、正丁基、烯丙基或苄基；所述R1和R2均为甲基时最优；X-为负离子，包括但不限于溴负离子、碘负离子或三氟甲磺酸根负离子；所述X-为碘负离子时最优。
在本发明提供的合成方法中，所述式II化合物为醛类化合物，其R为芳基或烷基；所述芳基优选为苯基、取代苯基、萘基、取代萘基、蒽基、取代蒽基、芳杂环基、取代芳杂环基、苯并芳杂环基或取代苯并芳杂环基；所述芳杂环基优选为吡啶基、呋喃基、噻吩基或吡咯基；所述苯并芳杂环基优选为喹啉基、苯并呋喃基、苯并噻吩基、咔唑基或吲哚基；所述烷基优选为链状烷基或环状烷基。
在本发明提供的合成方法中，所述式II化合物具体可选择对溴苯甲醛、对甲氧基苯甲醛、2-甲基苯甲醛、3-硝基苯甲醛、1,3-苯并二氧-4-甲醛、2-萘甲醛、9-蒽甲醛、9-乙基-9H-卡巴唑-2-羧醛、3-醛基苯并呋喃、3-乙酰基噻吩、8-甲酰基-7-羟基-4-甲基香豆素、苯丙醛、2-苯基丙醛、正辛醛、环己烷基甲醛、四氢吡喃-4-甲醛、1-叔丁氧羰基哌啶-4-甲醛或香茅醛。
在本发明提供的合成方法中，所述碱性试剂优选为有机碱和/或无机碱，包括但不限于氢氧化钠、氢氧化钾、叔丁醇钾、醋酸钾、碳酸钾、三乙胺和三乙烯二胺(DABCO)中的一种或多种；所述碱性试剂为三乙烯二胺(DABCO)时最优。
在本发明提供的合成方法中，所述溶剂优选为醇类溶剂，包括但不限于甲醇、乙醇和异丙醇中的一种或多种；所述溶剂为甲醇时最优。
在本发明提供的合成方法中，所述式I化合物、式II化合物和碱性试剂的摩尔比优选为(1～1.2):1:(0.2～0.6)，更优选为1.1:1:0.4。
在本发明提供的合成方法中，所述加热反应优选在密闭条件下进行，所使用的反应器优选为封管；所述加热反应的温度优选为80～120℃，更优选为100℃；所述加热反应的时间优选为6～15h，更优选为10h。
在本发明提供的合成方法中，所述加热反应结束后，优选对得到的反应产物进行除溶剂和纯化。其中，所述除溶剂之前优选先进行冷却；所述除溶剂的方式优选为减压蒸馏；所述纯化的方式优选为硅胶柱层析。
本发明提供的合成方法以托品酮季铵盐(式I)和醛类化合物(式II)为原料，在碱性试剂的存在下，仅通过加热即可进行反应而生成2-取代环庚三烯酮类化合物(式III)。本发明提供的合成方法具有原料廉价易得、操作简便、无需惰性气体保护、后处理简单、官能团兼容性好、产率高、位点选择性高的优点，且该方法放大至克级，产率依然可以保持，容易产业化。
为更清楚起见，下面通过以下实施例进行详细说明。
实施例1
按照如下反应式，合成2-取代环庚三烯酮类化合物：
具体合成过程为：在室温下，向装有磁力搅拌子的10毫升封管中装入托品酮季铵盐1a(0.22毫摩尔)、对溴苯甲醛2a(0.2毫摩尔)、三乙烯二胺(0.08毫摩尔)和甲醇(1.2毫升)，油浴加热至100℃，搅拌10小时，冷却至室温，减压浓缩，残余物经硅胶柱层析分离(洗脱剂为石油醚/乙酸乙酯＝5:1)，得到目标产物3a，产率为89％。
所得产物3a核磁谱图数据为：1H NMR(500MHz,CDCl3)δ7.42-7.39(m,2H),7.15-7.08(m,5H),6.96-6.91(m,2H),3.91(s,2H)；13C NMR(125MHz,CDCl3)δ186.5,154.1,140.8,138.2,135.8,135.8,133.8,133.2,131.7,131.2,120.4,40.3；HRMS(ESI)calcd forC14H12BrO+(M+H)+275.0066,found275.0070。
实施例1的放大制备：
在室温下，向装有磁力搅拌子的100毫升封管中装入托品酮季铵盐1a(6.6毫摩尔)、对溴苯甲醛2a(6.0毫摩尔)、三乙烯二胺(2.4毫摩尔)和甲醇(20毫升)，油浴加热至100℃，搅拌10小时，冷却至室温，减压浓缩，残余物经硅胶柱层析分离(洗脱剂为石油醚/乙酸乙酯＝5:1)，得到目标产物3a，产率为84％。
实施例2
按照如下反应式，合成2-取代环庚三烯酮类化合物：
具体合成过程为：在室温下，向装有磁力搅拌子的10毫升封管中装入托品酮季铵盐1a(0.22毫摩尔)、对甲氧基苯甲醛2b(0.2毫摩尔)、三乙烯二胺(0.08毫摩尔)和甲醇(1.2毫升)，油浴加热至100℃，搅拌10小时，冷却至室温，减压浓缩，残余物经硅胶柱层析分离(洗脱剂为石油醚/乙酸乙酯＝5:1)，得到目标产物3b，产率为69％。
所得产物3b核磁谱图数据为：1H NMR(500MHz,CDCl3)δ7.16(d,J＝8.5Hz,2H),7.12-7.11(m,2H),7.09-7.07(m,1H),6.94-6.90(m,2H),6.86-6.84(m,2H),3.91(s,2H),3.79(s,3H)；13C NMR(125MHz,CDCl3)δ186.9,158.4,155.3,140.7,135.7,135.6,133.9,132.8,131.1,130.7,114.1,55.3,39.8；HRMS(ESI)calcd for C15H15O2 +(M+H)+227.1067,found 227.1072。
实施例3
按照如下反应式，合成2-取代环庚三烯酮类化合物：
具体合成过程为：在室温下，向装有磁力搅拌子的10毫升封管中装入托品酮季铵盐1a(0.22毫摩尔)、2-甲基苯甲醛2c(0.2毫摩尔)、三乙烯二胺(0.08毫摩尔)和甲醇(1.2毫升)，油浴加热至100℃，搅拌10小时，冷却至室温，减压浓缩，残余物经硅胶柱层析分离(洗脱剂为石油醚/乙酸乙酯＝5:1)，得到目标产物3c，产率为86％。
所得产物3c核磁谱图数据为：1H NMR(400MHz,CDCl3)δ7.21-7.16(m,3H),7.15-7.09(m,3H),6.93-6.83(m,2H),6.79-6.75(m,1H),3.96(s,2H),2.18(s,3H)；13C NMR(100MHz,CDCl3)δ187.0,154.2,140.2,137.2,137.2,135.7,134.6,133.8,132.7,130.7,130.5,127.0,126.3,37.9,19.5；HRMS(ESI)calcd for C15H15O+(M+H)+211.1117,found211.1121。
实施例4
按照如下反应式，合成2-取代环庚三烯酮类化合物：
具体合成过程为：在室温下，向装有磁力搅拌子的10毫升封管中装入托品酮季铵盐1a(0.22毫摩尔)、3-硝基苯甲醛2d(0.2毫摩尔)、三乙烯二胺(0.08毫摩尔)和甲醇(1.2毫升)，油浴加热至100℃，搅拌10小时，冷却至室温，减压浓缩，残余物经硅胶柱层析分离(洗脱剂为石油醚/乙酸乙酯＝2:1)，得到目标产物3d，产率为54％。
所得产物3d核磁谱图数据为：1H NMR(500MHz,CDCl3)δ8.11-8.07(m,2H),7.66(d,J＝7.5Hz,1H),7.46(t,J＝8.0Hz,1H),7.27-7.25(m,1H),7.18-7.14(m,1H),7.10(d,J＝12.0Hz,1H),7.02-6.97(m,2H),4.05(s,2H)；13CNMR(125MHz,CDCl3)δ186.4,152.9,148.4,141.3,141.2,136.3,136.0,135.9,133.8,133.7,129.4,124.0,121.8,41.0；HRMS(ESI)calcd for C14H12NO3 +(M+H)+242.0812,found 242.0816。
实施例5
按照如下反应式，合成2-取代环庚三烯酮类化合物：
具体合成过程为：在室温下，向装有磁力搅拌子的10毫升封管中装入托品酮季铵盐1a(0.22毫摩尔)、1,3-苯并二氧-4-甲醛2e(0.2毫摩尔)、三乙烯二胺(0.08毫摩尔)和甲醇(1.2毫升)，油浴加热至100℃，搅拌10小时，冷却至室温，减压浓缩，残余物经硅胶柱层析分离(洗脱剂为石油醚/乙酸乙酯＝5:1)，得到目标产物3e，产率为82％。
所得产物3e核磁谱图数据为：1H NMR(500MHz,CDCl3)δ7.15-7.07(m,3H),6.91-6.90(m,2H),6.78-6.70(m,3H),5.90(s,2H),3.92(s,2H)；13C NMR(125MHz,CDCl3)δ186.6,152.9,147.2,146.0,140.5,135.5,135.2,133.7,132.9,123.6,121.6,120.3,107.1,100.6,34.1；HRMS(ESI)calcd for C15H15O2 +(M+H)+241.0859,found 241.0864。
实施例6
按照如下反应式，合成2-取代环庚三烯酮类化合物：
具体合成过程为：在室温下，向装有磁力搅拌子的10毫升封管中装入托品酮季铵盐1a(0.22毫摩尔)、2-萘甲醛2f(0.2毫摩尔)、三乙烯二胺(0.08毫摩尔)和甲醇(1.2毫升)，油浴加热至100℃，搅拌10小时，冷却至室温，减压浓缩，残余物经硅胶柱层析分离(洗脱剂为石油醚/乙酸乙酯＝5:1)，得到目标产物3f，产率为84％。
所得产物3f核磁谱图数据为：1H NMR(400MHz,CDCl3)δ7.78(t,J＝8.8Hz,3H),7.69(s,1H),7.47-7.40(m,2H),7.34(dd,J＝8.6,1.8Hz,1H),7.14-7.06(m,3H),6.90-6.82(m,2H),4.12(s,2H)；13C NMR(100MHz,CDCl3)δ186.8,154.8,140.8,136.7,135.9,135.7,133.8,133.7,133.0,132.3,128.3,128.1,128.1,127.7,127.7,126.1,125.6,40.7；HRMS(ESI)calcd for C18H15O+(M+H)+247.1117,found 247.1121。
实施例7
按照如下反应式，合成2-取代环庚三烯酮类化合物：
具体合成过程为：在室温下，向装有磁力搅拌子的10毫升封管中装入托品酮季铵盐1a(0.22毫摩尔)、9-蒽甲醛2g(0.2毫摩尔)、三乙烯二胺(0.08毫摩尔)和甲醇(1.2毫升)，油浴加热至100℃，搅拌10小时，冷却至室温，减压浓缩，残余物经硅胶柱层析分离(洗脱剂为石油醚/乙酸乙酯＝5:1)，得到目标产物3g，产率为56％。
所得产物3g核磁谱图数据为：1H NMR(500MHz,CDCl3)δ8.47(s,1H),8.07-8.05(m,2H),7.99(d,J＝8.0Hz,2H),7.49-7.44(m,4H),7.35(d,J＝12.0Hz,1H),7.21(dd,J＝12.0,8.0Hz,1H),6.87-6.83(m,1H),6.60(t,J＝10Hz,1H),6.48(d,J＝9.0Hz,1H),4.96(s,2H)；13C NMR(125MHz,CDCl3)δ187.1,154.4,140.3,136.2,135.4,134.2,133.0,131.8,130.9,130.7,129.3,127.2,126.4,125.3,124.6,32.2；HRMS(ESI)calcd for C22H17O+(M+H)+297.1274,found 297.1274。
实施例8
按照如下反应式，合成2-取代环庚三烯酮类化合物：
具体合成过程为：在室温下，向装有磁力搅拌子的10毫升封管中装入托品酮季铵盐1a(0.22毫摩尔)、9-乙基-9H-卡巴唑-2-羧醛2h(0.2毫摩尔)、三乙烯二胺(0.08毫摩尔)和甲醇(1.2毫升)，油浴加热至100℃，搅拌10小时，冷却至室温，减压浓缩，残余物经硅胶柱层析分离(洗脱剂为石油醚/乙酸乙酯＝3:1)，得到目标产物3h，产率为68％。
所得产物3h核磁谱图数据为：1H NMR(500MHz,CDCl3)δ8.02(d,J＝7.5Hz,1H),7.93(s,1H),7.39(t,J＝7.5Hz,1H),7.31-7.25(m,3H),7.16(t,J＝7.5Hz,1H),7.08-6.96(m,3H),6.74-6.73(m,2H),4.23(q,J＝7.2Hz,2H),4.12(s,2H),1.33(t,J＝7.0Hz,3H)；13C NMR(125MHz,CDCl3)δ186.8,155.7,140.5,140.1,138.8,135.5,135.4,133.7,132.5,129.2,127.4,125.6,123.1,122.6,121.2,120.4,118.7,108.5,108.4,40.4,37.4,13.8；HRMS(ESI)calcd for C22H20NO+(M+H)+314.1539,found 314.1543。
实施例9
按照如下反应式，合成2-取代环庚三烯酮类化合物：
具体合成过程为：在室温下，向装有磁力搅拌子的10毫升封管中装入托品酮季铵盐1a(0.22毫摩尔)、3-醛基苯并呋喃2i(0.2毫摩尔)、三乙烯二胺(0.08毫摩尔)和甲醇(1.2毫升)，油浴加热至100℃，搅拌10小时，冷却至室温，减压浓缩，残余物经硅胶柱层析分离(洗脱剂为石油醚/乙酸乙酯＝3:1)，得到目标产物3i，产率为76％。
所得产物3i核磁谱图数据为：1H NMR(500MHz,CDCl3)δ7.54(s,1H),7.46(d,J＝8.0Hz,1H),7.43(d,J＝7.5Hz,1H),7.27(t,J＝7.8Hz,1H),7.20-7.14(m,2H),7.12-7.08(m,2H),6.89-6.81(m,2H),4.02(s,2H)；13C NMR(125MHz,CDCl3)δ186.7,155.4,152.5,143.2,140.5,135.7,135.0,133.7,133.1,127.8,124.3,122.5,119.9,117.3,111.6,28.3；HRMS(ESI)calcd for C16H13O2 +(M+H)+237.0910,found 237.0915。
实施例10
按照如下反应式，合成2-取代环庚三烯酮类化合物：
具体合成过程为：在室温下，向装有磁力搅拌子的10毫升封管中装入托品酮季铵盐1a(0.22毫摩尔)、3-乙酰基噻吩2j(0.2毫摩尔)、三乙烯二胺(0.08毫摩尔)和甲醇(1.2毫升)，油浴加热至100℃，搅拌10小时，冷却至室温，减压浓缩，残余物经硅胶柱层析分离(洗脱剂为石油醚/乙酸乙酯＝5:1)，得到目标产物3j，产率为65％。
所得产物3j核磁谱图数据为：1H NMR(500MHz,CDCl3)δ7.28-7.27(m,1H),7.14-7.12(m,3H),7.07(d,J＝2.0Hz,1H),6.97-6.92(m,3H),3.99(s,2H)；13C NMR(125MHz,CDCl3)δ186.8,154.3,140.8,139.1,135.7,135.5,133.9,133.1,129.0,125.8,122.6,35.2；HRMS(EI)calcd for C12H10OS+(M+)202.0447,found 202.0444。
实施例11
按照如下反应式，合成2-取代环庚三烯酮类化合物：
具体合成过程为：在室温下，向装有磁力搅拌子的10毫升封管中装入托品酮季铵盐1a(0.22毫摩尔)、8-甲酰基-7-羟基-4-甲基香豆素2k(0.2毫摩尔)、三乙烯二胺(0.08毫摩尔)和甲醇(1.2毫升)，油浴加热至100℃，搅拌10小时，冷却至室温，减压浓缩，残余物经硅胶柱层析分离(洗脱剂为石油醚/乙酸乙酯＝3:1)，得到目标产物3k，产率为52％。
所得产物3k核磁谱图数据为：1H NMR(500MHz,CDCl3)δ11.11(s,1H),8.34(d,J＝9.0Hz,1H),7.41-7.28(m,4H),7.16(t,J＝9.3Hz,1H),6.92(d,J＝9.0Hz,1H),6.10(s,1H),4.13(s,2H),2.38(s,3H)；13C NMR(125MHz,CDCl3)δ188.8,161.4,159.9,153.7,152.2,141.0,140.9,138.3,136.1,135.3,124.3,115.1,113.1,112.8,110.80,29.9,19.0；HRMS(ESI)calcd for C18H15O4 +(M+H)+295.0965,found 295.0962。
实施例12
按照如下反应式，合成2-取代环庚三烯酮类化合物：
具体合成过程为：在室温下，向装有磁力搅拌子的10毫升封管中装入托品酮季铵盐1a(0.22毫摩尔)、苯丙醛2l(0.2毫摩尔)、三乙烯二胺(0.08毫摩尔)和甲醇(1.2毫升)，油浴加热至100℃，搅拌10小时，冷却至室温，减压浓缩，残余物经硅胶柱层析分离(洗脱剂为石油醚/乙酸乙酯＝5:1)，得到目标产物3l，产率为77％。
所得产物3l核磁谱图数据为：1H NMR(500MHz,CDCl3)δ7.29-7.26(m,2H),7.23-7.16(m,4H),7.12-7.06(m,2H),6.96-6.88(m,2H),2.71-2.68(m,4H),1.93-1.87(m,2H)；13CNMR(125MHz,CDCl3)δ187.1,155.8,142.2,140.5,135.6,135.1,134.0,132.8,128.5,128.4,125.9,35.9,35.4,30.5；HRMS(EI)calcd for C16H16O+(M+)224.1196,found224.1193。
实施例13
按照如下反应式，合成2-取代环庚三烯酮类化合物：
具体合成过程为：在室温下，向装有磁力搅拌子的10毫升封管中装入托品酮季铵盐1a(0.22毫摩尔)、2-苯基丙醛2m(0.2毫摩尔)、三乙烯二胺(0.08毫摩尔)和甲醇(1.2毫升)，油浴加热至100℃，搅拌10小时，冷却至室温，减压浓缩，残余物经硅胶柱层析分离(洗脱剂为石油醚/乙酸乙酯＝5:1)，得到目标产物3m，产率为77％。
所得产物3m核磁谱图数据为：1H NMR(500MHz,CDCl3)δ7.27-7.24(m,2H),7.18-7.14(m,3H),7.06(d,J＝4.0Hz,2H),6.93(d,J＝9.0Hz,1H),6.86-6.82(m,1H),6.80-6.76(m,1H),3.16(sext,J＝7.1Hz,1H),2.95(dd,J＝12.5,7.0Hz,1H),2.82(dd,J＝12.5,7.5Hz,1H),1.30(d,J＝7.0Hz,3H)；13CNMR(125MHz,CDCl3)δ187.2,153.9,146.7,140.5,136.3,135.5,133.7,132.8,128.4,127.2,126.1,45.1,38.6,21.6；HRMS(EI)calcd forC16H16O+(M+)224.1196,found 224.1193。
实施例14
按照如下反应式，合成2-取代环庚三烯酮类化合物：
具体合成过程为：在室温下，向装有磁力搅拌子的10毫升封管中装入托品酮季铵盐1a(0.22毫摩尔)、正辛醛2n(0.2毫摩尔)、三乙烯二胺(0.08毫摩尔)和甲醇(1.2毫升)，油浴加热至100℃，搅拌10小时，冷却至室温，减压浓缩，残余物经硅胶柱层析分离(洗脱剂为石油醚/乙酸乙酯＝5:1)，得到目标产物3n，产率为68％。
所得产物3n核磁谱图数据为：1H NMR(500MHz,CDCl3)δ7.25(d,J＝8.5Hz,1H),7.12-7.05(m,2H),6.98-6.89(m,2H),2.64(t,J＝7.8Hz,2H),1.59-1.53(m,2H),1.37-1.26(m,10H),0.89-0.86(m,3H)；13C NMR(125MHz,CDCl3)δ187.2,156.4,140.4,135.4,134.8,134.0,132.5,35.7,32.0,29.8,29.6,29.4,29.0,22.8,14.2；HRMS(EI)calcd for C15H22O+(M+)218.1665,found 218.1662。
实施例15
按照如下反应式，合成2-取代环庚三烯酮类化合物：
具体合成过程为：在室温下，向装有磁力搅拌子的10毫升封管中装入托品酮季铵盐1a(0.22毫摩尔)、环己烷基甲醛2o(0.2毫摩尔)、三乙烯二胺(0.08毫摩尔)和甲醇(1.2毫升)，油浴加热至100℃，搅拌10小时，冷却至室温，减压浓缩，残余物经硅胶柱层析分离(洗脱剂为石油醚/乙酸乙酯＝5:1)，得到目标产物3o，产率为53％。
所得产物3o核磁谱图数据为：1H NMR(500MHz,CDCl3)δ7.21(d,J＝8.5Hz,1H),7.13-7.07(m,2H),6.98-6.90(m,2H),2.54(d,J＝7.0Hz,2H),1.69-1.61(m,6H),1.26-1.10(m,3H),0.95(q,J＝10.8Hz,2H)；13C NMR(125MHz,CDCl3)δ187.3,154.8,140.4,136.1,135.5,133.9,132.7,43.8,37.0,33.6,26.6,26.4；HRMS(EI)calcd for C14H18O+(M+)202.1352,found 202.1349。
实施例16
按照如下反应式，合成2-取代环庚三烯酮类化合物：
具体合成过程为：在室温下，向装有磁力搅拌子的10毫升封管中装入托品酮季铵盐1a(0.22毫摩尔)、四氢吡喃-4-甲醛2p(0.2毫摩尔)、三乙烯二胺(0.08毫摩尔)和甲醇(1.2毫升)，油浴加热至100℃，搅拌10小时，冷却至室温，减压浓缩，残余物经硅胶柱层析分离(洗脱剂为石油醚/乙酸乙酯＝5:1)，得到目标产物3p，产率为59％。
所得产物3p核磁谱图数据为：1HNMR(500MHz,CDCl3)δ7.22-7.20(m,1H),7.13-7.09(m,1H),7.05(d,J＝12.0Hz,1H),6.97-6.91(m,2H),3.93(dd,J＝11.0,4.0Hz,2H),3.34(td,J＝11.8,1.5Hz,2H),2.59(d,J＝7.0Hz,2H),1.97-1.88(m,1H),1.57(dd,J＝13.0,1.5Hz,2H),1.34(qd,J＝12.3,4.5Hz,2H)；13C NMR(125MHz,CDCl3)δ187.2,153.4,140.6,136.2,135.5,133.6,133.0,68.0,43.5,33.9,33.3；HRMS(ESI)calcd for C13H17O2 +(M+H)+205.1223,found205.1227。
实施例17
按照如下反应式，合成2-取代环庚三烯酮类化合物：
具体合成过程为：在室温下，向装有磁力搅拌子的10毫升封管中装入托品酮季铵盐1a(0.22毫摩尔)、1-叔丁氧羰基哌啶-4-甲醛2q(0.2毫摩尔)、三乙烯二胺(0.08毫摩尔)和甲醇(1.2毫升)，油浴加热至100℃，搅拌10小时，冷却至室温，减压浓缩，残余物经硅胶柱层析分离，得到目标产物3q(洗脱剂为石油醚/乙酸乙酯＝2:1)，产率为49％。
所得产物3q核磁谱图数据为：1H NMR(500MHz,CDCl3)δ7.20(dd,J＝7.5,2.0Hz,1H),7.13-7.09(m,1H),7.05(d,J＝12.0Hz,1H),6.97-6.91(m,2H),4.06(s,2H),2.64-2.58(m,4H),1.88-1.79(m,1H),1.62(d,J＝13.5Hz,2H),1.45(s,9H),1.15(qd,J＝12.4,4.3Hz,2H)；13C NMR(125MHz,CDCl3)δ187.1,154.9,153.5,140.6,136.2,135.5,133.6,132.9,79.2,43.1,34.9,32.3,28.5；HRMS(ESI)calcd for C18H26NO3 +(M+H)+304.1907,found304.1910。
实施例18
按照如下反应式，合成2-取代环庚三烯酮类化合物：
具体合成过程为：在室温下，向装有磁力搅拌子的10毫升封管中装入托品酮季铵盐1a(0.22毫摩尔)、香茅醛2r(0.2毫摩尔)、三乙烯二胺(0.08毫摩尔)和甲醇(1.2毫升)，油浴加热至100℃，搅拌10小时，冷却至室温，减压浓缩，残余物经硅胶柱层析分离(洗脱剂为石油醚/乙酸乙酯＝2:1)，得到目标产物3r，产率为71％。
所得产物3r核磁谱图数据为：1H NMR(500MHz,CDCl3)δ7.24(d,J＝8.5Hz,1H),7.11-7.03(m,2H),6.97-6.87(m,2H),5.10(t,J＝7.3Hz,1H),2.72-2.58(m,2H),2.05-1.92(m,2H),1.68(s,3H),1.60(s,3H),1.58-1.47(m,2H),1.43-1.34(m,2H),1.23-1.15(m,1H),0.95(d,J＝6.5Hz,3H)；13C NMR(125MHz,CDCl3)δ187.0,156.7,140.3,135.3,134.6,133.9,132.4,131.1,124.9,36.9,36.2,33.2,32.6,25.8,25.5,19.5,17.7；HRMS(EI)calcd forC17H24O+(M+)244.1822,found 244.1820。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (10)

1.一种2-取代环庚三烯酮类化合物的合成方法，包括以下步骤：
在碱性试剂存在下，将式I化合物与式II化合物在溶剂中加热反应，得到式III结构的2-取代环庚三烯酮类化合物；
其中，R1和R2独立的选择甲基、正丁基、烯丙基或苄基；X-为负离子；R为芳基或烷基。
2.根据权利要求1所述的合成方法，其特征在于，所述R1和R2均为甲基。
3.根据权利要求1所述的合成方法，其特征在于，所述芳基为苯基、取代苯基、萘基、取代萘基、蒽基、取代蒽基、芳杂环基、取代芳杂环基、苯并芳杂环基或取代苯并芳杂环基；所述烷基为链状烷基或环状烷基。
4.根据权利要求3所述的合成方法，其特征在于，所述芳杂环基为吡啶基、呋喃基、噻吩基或吡咯基；所述苯并芳杂环基为喹啉基、苯并呋喃基、苯并噻吩基、咔唑基或吲哚基。
5.根据权利要求1所述的合成方法，其特征在于，所述负离子为溴负离子、碘负离子或三氟甲磺酸根负离子。
6.根据权利要求1所述的合成方法，其特征在于，所述碱性试剂为有机碱和/或无机碱。
7.根据权利要求1所述的合成方法，其特征在于，所述式I化合物、式II化合物和碱性试剂的摩尔比为(1～1.2):1:(0.2～0.6)。
8.根据权利要求1所述的合成方法，其特征在于，所述加热反应的温度为80～120℃；所述加热反应的时间为6～15h。
9.根据权利要求1所述的合成方法，其特征在于，所述溶剂为醇类溶剂。
10.根据权利要求1所述的合成方法，其特征在于，还包括：所述加热反应结束后，对得到的反应产物进行除溶剂和纯化。
CN202310465066.7A 2023-04-26 2023-04-26 一种2-取代环庚三烯酮类化合物的合成方法 Pending CN116478026A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310465066.7A CN116478026A (zh) 2023-04-26 2023-04-26 一种2-取代环庚三烯酮类化合物的合成方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310465066.7A CN116478026A (zh) 2023-04-26 2023-04-26 一种2-取代环庚三烯酮类化合物的合成方法

Publications (1)

Publication Number Publication Date
CN116478026A true CN116478026A (zh) 2023-07-25

Family

ID=87213509

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310465066.7A Pending CN116478026A (zh) 2023-04-26 2023-04-26 一种2-取代环庚三烯酮类化合物的合成方法

Country Status (1)

Country Link
CN (1) CN116478026A (zh)

Similar Documents

Publication Publication Date Title
Yang et al. Squaramide-catalysed enantio-and diastereoselective sulfa-Michael addition of thioacetic acid to α, β-disubstituted nitroalkenes
Nagao et al. Asymmetric trifluoromethylation of ketones with (trifluoromethyl) trimethylsilane catalyzed by chiral quaternary ammonium phenoxides
EP2931708B1 (fr) Composes cyclopropylboroniques, leur procede de preparation et leur utilisation
Chen et al. Synthesis of axially chiral C10-BridgePHOS oxides and their use as organocatalysts in enantioselective allylations of aldehydes
CN108690030A (zh) 具有光学活性的吡咯硫酮结构的螺环氧化吲哚类化合物及其合成方法
Sá et al. Synthesis of allylic thiocyanates and novel 1, 3-thiazin-4-ones from 2-(bromomethyl) alkenoates and S-nucleophiles in aqueous medium
Wang et al. An efficient multigram synthesis of alkannin and shikonin
JP4845266B2 (ja) ５−（α−ヒドロキシアルキル）ベンゾ［１，３］ジオキソールの合成方法
Yamazaki et al. Enantioselective Friedel–Crafts reactions of ethenetricarboxylates and substituted pyrroles and furans and intramolecular reaction of benzene derivatives
CN116478026A (zh) 一种2-取代环庚三烯酮类化合物的合成方法
JP2009515840A (ja) エスシタロプラムの製造方法
RU2282633C1 (ru) СПОСОБ ПОЛУЧЕНИЯ 1,11-ДИАЛКИЛ-3,5-ДИГИДРОФУРО[2',3':3,4]ЦИКЛОГЕПТА[c]ИЗОХРОМЕНОВ
CN110240572B (zh) 一种反式-1,1-环丙烷二羧酸酯的合成方法
JP4906711B2 (ja) ３−シクロペンチルオキシ−４−メトキシベンズアルデヒドの製造方法
CN103804273B (zh) 氧化吲哚与茚三酮双季碳拼接衍生物及其制备方法
CN115093315B (zh) 一种2-亚苄基-3-环己烯酮化合物的合成方法
CN114773382B (zh) 一类手性化合物含吲哚/咔唑骨架α-硅氧基酮衍生物、制备方法及应用
Meng et al. Organocatalytic domino reaction of salicyl N-thiophosphoryl imines and methyl vinyl ketone initiated by an aza-MBH reaction with bifunctional phosphine catalysts
CN107892669A (zh) 一种通过借氢反应合成喹啉衍生物的方法
CN113234061B (zh) 一种双取代螺环芳烃的合成方法
KR100941173B1 (ko) 다이하이드로퓨란 유도체와 금 촉매를 이용한 이의제조방법
JP6498614B2 (ja) 光学活性カルボン酸エステルの製造方法
KR101957304B1 (ko) 보란촉매 하에 퓨란 유도체로부터 실란 유도체의 제조방법
JP5213472B2 (ja) １−アリール−３，４−ジヒドロ−１ｈ−ナフタレン−２−オンの製造方法
KR101742022B1 (ko) 신규 바이아릴 화합물 및 벤젠고리화 반응을 이용한 이의 제조방법

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