CN114656431A - 一种α,β-不饱和酮类化合物及其制备方法、应用 - Google Patents

一种α,β-不饱和酮类化合物及其制备方法、应用 Download PDF

Info

Publication number
CN114656431A
CN114656431A CN202210389352.5A CN202210389352A CN114656431A CN 114656431 A CN114656431 A CN 114656431A CN 202210389352 A CN202210389352 A CN 202210389352A CN 114656431 A CN114656431 A CN 114656431A
Authority
CN
China
Prior art keywords
compound
unsaturated ketone
beta
alpha
reaction
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.)
Granted
Application number
CN202210389352.5A
Other languages
English (en)
Other versions
CN114656431B (zh
Inventor
张维
艾文英
金海涛
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.)
Zhejiang Tangneng Technology Co ltd
Original Assignee
Zhejiang Tangneng Technology Co ltd
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 Zhejiang Tangneng Technology Co ltd filed Critical Zhejiang Tangneng Technology Co ltd
Publication of CN114656431A publication Critical patent/CN114656431A/zh
Application granted granted Critical
Publication of CN114656431B publication Critical patent/CN114656431B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/42—Singly bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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
    • C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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 with substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/333—Radicals substituted by oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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
    • C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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 with substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/335—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
    • 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
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • 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
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • 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
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/16—Radicals substituted by singly bound hetero atoms other than halogen by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

本申请公开了一种α,β‑不饱和酮类化合物及其制备方法、应用，所述α,β‑不饱和酮类化合物选自具有式I所示结构式的化合物、具有式II所示结构式的化合物中的至少一种。本发明的α,β‑不饱和酮类化合物作为有机缓蚀剂对碳钢表现出了极强的抗腐蚀效果。对碳钢处理后，其腐蚀速率较已知水溶性咪唑啉季铵盐缓蚀剂的腐蚀速率减小近5倍。

Description

一种α,β-不饱和酮类化合物及其制备方法、应用
技术领域
本申请涉及一种α,β-不饱和酮类化合物及其制备方法、应用，属于缓蚀剂技术领域。
背景技术
工业生产中，在对大型钢铁设施喷涂防腐涂层之前，需要对其表面进行除锈喷砂处理。然而传统的干喷砂工艺往往伴随粉尘及噪音污染。20世纪80年代水喷砂工艺引入国内，相比传统干喷砂具有良好的环保性，但受限于除锈后易形成二次返锈，因此难以大规模推广应用。近年来，环保法规相继出台，传统干喷砂工艺的使用严格受限，水喷砂工艺则因其环保优势再次走进大众视野。水喷砂工艺目前主要面临以下两个问题：第一，水喷砂处理后，钢铁表面湿度大，因此极易返锈；第二，为阻止水喷砂后返锈，通常在水喷砂过程中加入缓蚀剂，而传统的无机缓蚀剂如亚硝酸盐、铬酸盐、磷酸盐、炔醇等极易对环境产生危害，目前正逐步被淘汰。
发明内容
根据本申请的一个方面，提供了一种α,β-不饱和酮类化合物及其制备方法和应用，所述α,β-不饱和酮类化合物具有芳香环、多重键及杂原子(N、O、S等)，可作为缓蚀剂使用，利用共轭π电子及杂原子中的孤对电子提高缓蚀剂的性能。这些缓蚀剂可以通过金属与杂原子之间的静电作用力或π-d电子相互作用紧密吸附在金属表层，从而把腐蚀介质与金属基底有效阻隔，实现高效防腐。
根据本申请的第一方面，提供了一种α,β-不饱和酮类化合物，所述α,β-不饱和酮类化合物选自具有式I所示结构式的化合物、具有式II所示结构式的化合物中的至少一种；
Figure BDA0003594970610000011
Figure BDA0003594970610000021
在式I、式II中，Y1选自亚甲基、N、O、S中的任一种；Y2选自次甲基、N中的任一种；
R1选自C1-C24的烷基中的任一种；
R2选自氨基、羟基、*-OSO3M、聚乙氧基醚基、取代的氨基、聚乙胺基、＊-NR3 +x1 -中的任一种；
M选自Na、K、Li中的任一种；
R3选自C1-C6的烷基、取代的C1-C6的烷基、C6-C12的芳基中的任一种；
X1选自卤素。
可选地，所述取代的氨基中的取代基选自C6-C12的芳基中的任一种。
可选地，所述聚乙氧基醚基中的乙氧基单元数为1～10；
所述聚乙胺基中的乙胺基单元数为1～10。
所述取代的C1-C6的烷基中的取代基选自C6-C12的芳基中的任一种。
根据本申请的第二方面，提供了一种上述α,β-不饱和酮类化合物的制备方法，所述制备方法包括：
将含有化合物i和化合物ii的混合物，在碱性物存在下反应I，得到所述α,β-不饱和酮类化合物P；
所述α,β-不饱和酮类化合物P中的R2为羟基；
所述化合物i选自具有式III所示结构式的化合物、具有式IV所示结构式的化合物中的任一种；
Figure BDA0003594970610000022
所述化合物ii选自具有式V所示结构式的化合物中的任一种；
Figure BDA0003594970610000023
或者，
(a)将所述α,β-不饱和酮类化合物P与卤代试剂混合，反应II，得到卤代的中间产物K；
(b)将所述卤代的中间产物K与含有R2的亲核试剂反应III，即可得到所述α,β-不饱和酮类化合物O；
所述α,β-不饱和酮类化合物O中的R2选自氨基、*-OSO3M、聚乙氧基醚基、取代的氨基、聚乙胺基、＊-NR3 +x1 -中的任一种；
或者，
将所述α,β-不饱和酮类化合物P与吡啶硫酸盐混合，反应IV，得到所述α,β-不饱和酮类化合物Q；
所述α,β-不饱和酮类化合物Q中的R2为*-OSO3M。
可选地，所述α,β-不饱和酮类化合物可从醛(3)和酮(4)类化合物出发来制备。首先，在溶剂醇类化合物和碱性水溶液存在下，向其中加入醛(3)和酮(4)，室温反应，制备化合物(5)。随后利用二氯亚砜将化合物(5)中的羟基进行氯代，制备氯代化合物(6)。最后利用亲核试剂如三乙胺、三丁胺、三苄胺、苯胺、三缩四乙二醇等对氯代物进行亲核取代，制备得到化合物(1)。其中，还可以利用吡啶硫酸盐对化合物(5)中的羟基直接硫酸盐化，制备得到符合通式(1)的硫酸盐化合物。
Figure BDA0003594970610000031
反应路线1：α,β-不饱和酮类有机缓蚀剂的制备路线
可选地，所述反应I的条件为：反应温度为20℃～30℃；反应时间为18h～24h；
所述反应II的条件为：反应温度为10℃～20℃；反应时间为0.5h～4h；
所述反应III的条件为：反应温度为50℃～100℃；反应时间为0.5h～5h；
所述反应IV的条件为：反应温度为20℃～30℃；反应时间为0.5h～2h。
可选地，在所述步骤(a)中，所述卤代试剂选自二氯亚砜、草酰氯、三氯氧磷、浓盐酸、三溴化磷中中的至少一种；
所述含有R2的亲核试剂选自三乙胺、三丁胺、三苄胺、苯胺、、二乙二醇、三甘醇、三丙二醇、三缩四乙二醇、五甘醇、八甘醇、N,N'-二(2-氨乙基)-1,3-丙二胺、二乙烯三胺、三乙烯四胺、1,8-二氨基-3,6-二氧杂辛烷中的至少一种。
可选地，所述化合物i和所述化合物ii的摩尔比为0.5-1:1-10；
在所述步骤(a)中，所述α,β-不饱和酮类化合物P、酰氯试剂和含有R2的亲核试剂的摩尔比为0.5-1:1-10:1-10；
所述α,β-不饱和酮类化合物P与吡啶硫酸盐的摩尔比为0.5-1:1-10。
可选地，所述碱性物选自氢氧化钠、氢氧化钾、碳酸氢钠、碳酸钠、碳酸钾、碳酸铯、氢化钠、磷酸钾中的至少一种。
根据本申请的最后一方面，提供了一种上述α,β-不饱和酮类化合物、根据上述方法制备得到的α,β-不饱和酮类化合物中的至少一种在作为缓蚀剂中的应用。
可选地，所述缓蚀剂用于碳钢防腐。
本申请中，C1～C6指所包含的碳原子数。
本申请中，“烷基”是由烷烃化合物分子上失去任意一个氢原子所形成的基团。所述烷烃化合物包括直链烷烃、支链烷烃、环烷烃、带有支链的环烷烃。
本申请中，“聚乙氧基醚基”指的是
Figure BDA0003594970610000041
n＝0,1,2…9。
本申请中，“聚乙胺基”指的是
Figure BDA0003594970610000042
n＝0,1,2…9。
本申请中，“芳基”是芳香族化合物分子上失去芳香环上一个氢原子所形成的基团；如甲苯失去苯环上甲基对位的氢原子所形成的对甲苯基。
本申请能产生的有益效果包括：
本发明的α,β-不饱和酮类化合物作为有机缓蚀剂对碳钢表现出了极强的抗腐蚀效果。通过采用静态失重法，将本发明中的α,β-不饱和酮类化合物与已知的水溶性咪唑啉季铵盐缓蚀剂对比，本发明缓蚀剂具有更强的防腐性能。对碳钢处理后，其腐蚀速率较已知水溶性咪唑啉季铵盐缓蚀剂的腐蚀速率减小近5倍。
具体实施方式
下面结合实施例详述本申请，但本申请并不局限于这些实施例。
如无特别说明，本申请的实施例中的原料和催化剂均通过商业途径购买。
实施例1(5-(羟甲基)呋喃-2-基)癸-1-烯-3-酮
Figure BDA0003594970610000051
合成步骤：5-羟甲基糠醛(100mg，1当量)，2-壬酮(5当量)，0.5M NaOH(0.57当量，0.9mL)，MeOH(0.9mL)，室温搅拌12小时，每隔5小时点板监测一次反应(用石油醚PE：乙酸乙酯EtOAc＝5：1监测)。待反应物5-羟甲基糠醛消失后，向其中加入乙酸乙酯100mL，用饱和食盐水洗涤、萃取三次，收集有机相，水相用乙酸乙酯萃取两次，合并有机相，加入无水硫酸镁或无水硫酸钠干燥，过滤除去干燥剂，浓缩有机相，在硅胶柱上，用石油醚：乙酸乙酯10：1～石油醚：乙酸乙酯5：1梯度洗脱得到纯化的目标产物。
实施例2
N，N-二乙基-N-((5-(3-氧代-1-烯-1-基)呋喃-2-基)甲基)氯化乙胺
Figure BDA0003594970610000052
步骤一：向实例1所得化合物(100mg，1当量)中加入二氯甲烷(1mL)得到混合液，向混合液中缓慢滴加二氯亚砜(1.1当量)，室温搅拌0.5小时，每隔0.5小时点板监测一次反应(用石油醚：乙酸乙酯10：1监测)。无反应物后，向反应液中滴加饱和碳酸氢钠水溶液，缓慢淬灭反应，直至反应液中没有气泡产生，向体系中加入50毫升二氯甲烷，用饱和碳酸氢钠水溶液、饱和食盐水洗涤该混合体系三次，合并三次的有机溶剂，干燥，过滤，浓缩有机相后即可得到氯代物粗品，直接用于下一步反应。
步骤二：向上一步所得到的氯代物粗品中加入乙腈溶剂(2mL)和三乙胺(1.2当量)，80℃反应3小时，每隔1.5小时监测一次反应(用石油醚：乙酸乙酯10：1监测氯代原料，用DCM：MeOH＝10：1监测季铵盐产品)，反应结束后，用旋转蒸发仪浓缩反应液，浓缩后，向浓缩液中加入二氯甲烷50mL，用饱和食盐水洗涤萃取三次，合并三次的有机相，干燥、过滤、浓缩。随后在硅胶柱上，用二氯甲烷：甲醇20：1洗脱得到纯化的目标产物。
实施例3(5-(3-氧代-1-烯-1-基)呋喃-2-基)硫酸钠盐
Figure BDA0003594970610000061
合成步骤：向实例1所得化合物(100mg，1当量)中分别加入吡啶三氧化硫复合物(1当量)和吡啶(3mL)，室温搅拌12小时，每隔1小时点板监测一次反应(用PE：EA＝5：1监测原料，用二氯甲烷DCM：甲醇MeOH＝10：1监测产物)。反应结束后，用旋转蒸发仪浓缩反应液(水浴温度65℃)，浓缩后，向浓缩液中加入二氯甲烷1mL，放入冰箱冷冻结晶(注意：不要震动)，约半小时后，取出，可观察到有大量结晶固体析出，在布氏漏斗中，用石油醚洗涤所得到的结晶，该结晶即为初步纯化的目标产物，随后在硅胶柱上，用二氯甲烷：甲醇20：1洗脱得到纯化的目标产物。
实施例4(5-(氨甲基)呋喃-2-基)癸-1-烯-3-酮
Figure BDA0003594970610000062
合成步骤：步骤一：将实例1所得化合物(100mg，1当量)溶解在二氯甲烷(4mL)中，冷却至0℃，随后向其中滴加三溴化磷(1.3当量)的二氯甲烷(4mL)溶液，进一步搅拌1小时，每隔0.5小时点板监测一次反应。反应结束后，用水洗涤，二氯甲烷萃取，无水硫酸钠干燥，溶剂蒸发后所得油状物即为溴代物粗品，无需进一步纯化，直接用于下一步反应。
步骤二：将步骤一所得溴代物溶于乙醚/乙醇(2mL：2mL)的混合溶液中，向其中滴加氨水(0.5mL)，室温下搅拌5小时。反应结束后，用水洗涤，二氯甲烷萃取，无水硫酸钠干燥，溶剂蒸发后所得油状物即为目标产物粗品，随后在硅胶柱上，用石油醚：乙酸乙酯1：1洗脱得到纯化的目标产物。
实施例5
(5-((2-((2-氨基乙基)氨基乙基)氨基)甲基)呋喃-2-基)癸-1-烯-3-酮
Figure BDA0003594970610000063
步骤一：向实例1所得化合物(100mg，1当量)中加入二氯甲烷(1mL)得到混合液，向混合液中缓慢滴加二氯亚砜(1.1当量)，室温搅拌0.5小时，每隔0.5小时点板监测一次反应(用石油醚：乙酸乙酯10：1监测)。反应结束后，向反应液中滴加饱和碳酸氢钠水溶液，缓慢淬灭反应，直至反应液中没有气泡产生，向体系中加入50毫升二氯甲烷，用饱和碳酸氢钠水溶液、饱和食盐水洗涤该混合体系三次，合并三次的有机溶剂，干燥，过滤，浓缩有机相后即可得到氯代物粗品，直接用于下一步反应。
步骤二：向上一步所得到的氯代物粗品中加入乙腈溶剂(2mL)和二乙烯三胺(1.1当量)，80℃反应3小时，每隔1.5小时监测一次反应，反应结束后，用旋转蒸发仪浓缩反应液，浓缩后，向浓缩液中加入二氯甲烷50mL，用饱和食盐水洗涤萃取三次，合并三次的有机相，干燥、过滤、浓缩。随后在硅胶柱上，用二氯甲烷：甲醇20：1洗脱得到纯化的目标产物。
实施例6
(5-((2-(2-羟基乙氧基)乙氧基)甲基)呋喃-2-基)癸-1-烯-3-酮
Figure BDA0003594970610000071
步骤一：向实例1所得化合物(100mg，1当量)中加入二氯甲烷(1mL)得到混合液，向混合液中缓慢滴加二氯亚砜(1.1当量)，室温搅拌0.5小时，每隔0.5小时点板监测一次反应(用石油醚：乙酸乙酯10：1监测)。反应结束后，向反应液中滴加饱和碳酸氢钠水溶液，缓慢淬灭反应，直至反应液中没有气泡产生，向体系中加入50毫升二氯甲烷，用饱和碳酸氢钠水溶液、饱和食盐水洗涤该混合体系三次，合并三次的有机溶剂，干燥，过滤，浓缩有机相后即可得到氯代物粗品，直接用于下一步反应。
步骤二：向上一步所得到的氯代物粗品中加入乙腈溶剂(2mL)和二乙二醇(1.1当量)，80℃反应3小时，每隔1.5小时监测一次反应，反应结束后，用旋转蒸发仪浓缩反应液，浓缩后，向浓缩液中加入二氯甲烷50mL，用饱和食盐水洗涤萃取三次，合并三次的有机相，干燥、过滤、浓缩。随后在硅胶柱上，用二氯甲烷：甲醇20：1洗脱得到纯化的目标产物。
实施例7(5-(羟甲基)吡咯-2-基)癸-1-烯-3-酮
Figure BDA0003594970610000081
合成步骤：5-(羟甲基)吡咯-2-甲醛(100mg，1当量)，2-壬酮(10当量)，0.5M NaOH(0.57当量，0.9mL)，MeOH(0.9mL)，室温搅拌12小时，每隔5小时点板监测一次反应(用石油醚PE：乙酸乙酯EtOAc＝5：1监测)。反应结束后，向其中加入乙酸乙酯100mL，用饱和食盐水洗涤、萃取三次，收集有机相，水相用乙酸乙酯萃取两次，合并有机相，加入无水硫酸镁或无水硫酸钠干燥，过滤除去干燥剂，浓缩有机相，在硅胶柱上，用石油醚：乙酸乙酯10：1～石油醚：乙酸乙酯5：1梯度洗脱得到纯化的目标产物。
实施例8 N，N-二乙基-N-((5-(3-氧代-1-烯-1-基)吡咯-2-基)甲基)氯化乙胺
Figure BDA0003594970610000082
步骤一：向实例7所得化合物(100mg，1当量)中加入二氯甲烷(1mL)得到混合液，向混合液中缓慢滴加二氯亚砜(1.1当量)，室温搅拌0.5小时，每隔0.5小时点板监测一次反应(用石油醚：乙酸乙酯10：1监测)。反应结束后，向反应液中滴加饱和碳酸氢钠水溶液，缓慢淬灭反应，直至反应液中没有气泡产生，向体系中加入50毫升二氯甲烷，用饱和碳酸氢钠水溶液、饱和食盐水洗涤该混合体系三次，合并三次的有机溶剂，干燥，过滤，浓缩有机相后即可得到氯代物粗品，直接用于下一步反应。步骤二：向上一步所得到的氯代物粗品中加入乙腈溶剂(2mL)和三乙胺(1.2当量)，80℃反应3小时，每隔1.5小时监测一次反应(用石油醚：乙酸乙酯10：1监测氯代原料，用DCM：MeOH＝10：1监测季铵盐产品)，反应结束后，用旋转蒸发仪浓缩反应液，浓缩后，向浓缩液中加入二氯甲烷50mL，用饱和食盐水洗涤萃取三次，合并三次的有机相，干燥、过滤、浓缩。随后在硅胶柱上，用二氯甲烷：甲醇20：1洗脱得到纯化的目标产物。
实施例9(5-(氨甲基)吡咯-2-基)癸-1-烯-3-酮
Figure BDA0003594970610000083
合成步骤：步骤一：将实例7所得化合物(100mg，1当量)溶解在二氯甲烷(4mL)中，冷却至0℃，随后向其中滴加三溴化磷(1.3当量)的二氯甲烷(4mL)溶液，进一步搅拌1小时，每隔0.5小时点板监测一次反应。反应结束后，用水洗涤，二氯甲烷萃取，无水硫酸钠干燥，溶剂蒸发后所得油状物即为溴代物粗品，无需进一步纯化，直接用于下一步反应。
步骤二：将步骤一所得溴代物溶于乙醚/乙醇(2mL：2mL)的混合溶液中，向其中滴加氨水(0.5mL)，室温下搅拌5小时。反应结束后，用水洗涤，二氯甲烷萃取，无水硫酸钠干燥，溶剂蒸发后所得油状物即为目标产物粗品，随后在硅胶柱上，用石油醚：乙酸乙酯1：1洗脱得到纯化的目标产物。
实施例10(5-(羟甲基)噻吩-2-基)癸-1-烯-3-酮
Figure BDA0003594970610000091
合成步骤：5-(羟甲基)-2-噻吩甲醛(100mg，1当量)，2-壬酮(5当量)，0.5M NaOH(0.57当量，0.9mL)，MeOH(0.9mL)，室温搅拌12小时，每隔5小时点板监测一次反应(用石油醚PE：乙酸乙酯EtOAc＝5：1监测)。反应结束后，向其中加入乙酸乙酯100mL，用饱和食盐水洗涤、萃取三次，收集有机相，水相用乙酸乙酯萃取两次，合并有机相，加入无水硫酸镁或无水硫酸钠干燥，过滤除去干燥剂，浓缩有机相，在硅胶柱上，用石油醚：乙酸乙酯10：1～石油醚：乙酸乙酯5：1梯度洗脱得到纯化的目标产物。
实施例11
(5-((2-((2-氨基乙基)氨基乙基)氨基)甲基)噻吩-2-基)癸-1-烯-3-酮
Figure BDA0003594970610000092
步骤一：向实例10所得化合物(100mg，1当量)中加入二氯甲烷(1mL)得到混合液，向混合液中缓慢滴加二氯亚砜(1.1当量)，室温搅拌0.5小时，每隔0.5小时点板监测一次反应(用石油醚：乙酸乙酯10：1监测)。反应结束后，向反应液中滴加饱和碳酸氢钠水溶液，缓慢淬灭反应，直至反应液中没有气泡产生，向体系中加入50毫升二氯甲烷，用饱和碳酸氢钠水溶液、饱和食盐水洗涤该混合体系三次，合并三次的有机溶剂，干燥，过滤，浓缩有机相后即可得到氯代物粗品，直接用于下一步反应。
步骤二：向上一步所得到的氯代物粗品中加入乙腈溶剂(2mL)和二乙烯三胺(1.1当量)，80℃反应3小时，每隔1.5小时监测一次反应，反应结束后，用旋转蒸发仪浓缩反应液，浓缩后，向浓缩液中加入二氯甲烷50mL，用饱和食盐水洗涤萃取三次，合并三次的有机相，干燥、过滤、浓缩。随后在硅胶柱上，用二氯甲烷：甲醇20：1洗脱得到纯化的目标产物。
实施例12
(5-(羟甲基)苯-2-基)癸-1-烯-3-酮
Figure BDA0003594970610000101
合成步骤：3-羟基苯甲醛(100mg，1当量)，2-壬酮(5当量)，0.5M NaOH(0.57当量，0.9mL)，MeOH(0.9mL)，室温搅拌12小时，每隔5小时点板监测一次反应(用石油醚PE：乙酸乙酯EtOAc＝5：1监测)。反应结束后，向其中加入乙酸乙酯100mL，用饱和食盐水洗涤、萃取三次，收集有机相，水相用乙酸乙酯萃取两次，合并有机相，加入无水硫酸镁或无水硫酸钠干燥，过滤除去干燥剂，浓缩有机相，在硅胶柱上，用石油醚：乙酸乙酯10：1～石油醚：乙酸乙酯5：1梯度洗脱得到纯化的目标产物。
实施例13
N，N-二乙基-N-((5-(3-氧代-1-烯-1-基)苯-2-基)甲基)氯化乙胺
Figure BDA0003594970610000102
步骤一：向实例12所得化合物(100mg，1当量)中加入二氯甲烷(1mL)得到混合液，向混合液中缓慢滴加二氯亚砜(1.1当量)，室温搅拌0.5小时，每隔0.5小时点板监测一次反应(用石油醚：乙酸乙酯10：1监测)。反应结束后，向反应液中滴加饱和碳酸氢钠水溶液，缓慢淬灭反应，直至反应液中没有气泡产生，向体系中加入50毫升二氯甲烷，用饱和碳酸氢钠水溶液、饱和食盐水洗涤该混合体系三次，合并三次的有机溶剂，干燥，过滤，浓缩有机相后即可得到氯代物粗品，直接用于下一步反应。
步骤二：向上一步所得到的氯代物粗品中加入乙腈溶剂(2mL)和三乙胺(1.2当量)，80℃反应3小时，每隔1.5小时监测一次反应(用石油醚：乙酸乙酯10：1监测氯代原料，用DCM：MeOH＝10：1监测季铵盐产品)，反应结束后，用旋转蒸发仪浓缩反应液，浓缩后，向浓缩液中加入二氯甲烷50mL，用饱和食盐水洗涤萃取三次，合并三次的有机相，干燥、过滤、浓缩。随后在硅胶柱上，用二氯甲烷：甲醇20：1洗脱得到纯化的目标产物。
实施例14
(6-(羟甲基)吡啶-2-基)癸-1-烯-3-酮
Figure BDA0003594970610000111
合成步骤：6-羟甲基吡啶甲醛(100mg，1当量)，2-壬酮(1当量)，0.5M NaOH(0.57当量，0.9mL)，MeOH(0.9mL)，室温搅拌12小时，每隔5小时点板监测一次反应(用石油醚PE：乙酸乙酯EtOAc＝5：1监测)。反应结束后，向其中加入乙酸乙酯100mL，用饱和食盐水洗涤、萃取三次，收集有机相，水相用乙酸乙酯萃取两次，合并有机相，加入无水硫酸镁或无水硫酸钠干燥，过滤除去干燥剂，浓缩有机相，在硅胶柱上，用石油醚：乙酸乙酯10：1～石油醚：乙酸乙酯5：1梯度洗脱得到纯化的目标产物。
实施例15(6-(氨甲基)吡啶-2-基)癸-1-烯-3-酮
Figure BDA0003594970610000112
合成步骤：步骤一：将实例14所得化合物(100mg，1当量)溶解在二氯甲烷(4mL)中，冷却至0℃，随后向其中滴加三溴化磷(1.3当量)的二氯甲烷(4mL)溶液，进一步搅拌1小时，每隔0.5小时点板监测一次反应。反应结束后，用水洗涤，二氯甲烷萃取，无水硫酸钠干燥，溶剂蒸发后所得油状物即为溴代物粗品，无需进一步纯化，直接用于下一步反应。
步骤二：将步骤一所得溴代物溶于乙醚/乙醇(2mL：2mL)的混合溶液中，向其中滴加氨水(0.5mL)，室温下搅拌5小时。反应结束后，用水洗涤，二氯甲烷萃取，无水硫酸钠干燥，溶剂蒸发后所得油状物即为目标产物粗品，随后在硅胶柱上，用石油醚：乙酸乙酯1：1洗脱得到纯化的目标产物。
实施例16静态失重评价
在500mL玻璃瓶中加入400mL 1mol/L的HCl溶液，升温至60℃，放入预处理好的Q235钢片腐蚀4h。腐蚀反应结束后，取出试片，参考SY5273-2014《油田采出水处理用缓蚀剂性能指标及评价方法》对试片进行试验后处理：在酸洗液中浸泡2min，用去污粉清洗，放入乙醇溶液中浸泡脱水，最后用冷风吹干，称质量，计算其腐蚀速率，并与空白和已知水溶性咪唑啉季铵盐缓蚀剂进行对照。
其中所述已知水溶性咪唑啉季铵盐缓蚀剂结构式为：
Figure BDA0003594970610000121
腐蚀速率计算按式如下：
Figure BDA0003594970610000122
式中:V为腐蚀速率，mm/a
ΔW为腐蚀前后试样的重量差，g；
s为试片的面积，cm2；
ρ为试片的密度，7.85g/cm3；
t为进行实验的时间，h；
碳钢规格为40*13*2(mm)
静态失重评价结果见表1。
表1静态失重评价结果
Figure BDA0003594970610000123
Figure BDA0003594970610000131
从上述表格数据可知，本发明的α,β-不饱和酮类化合物作为有机缓蚀剂对碳钢表现出了极强的抗腐蚀效果。对碳钢处理后，样品1-B、1-G的腐蚀速率均表现优秀，较已知水溶性咪唑啉季铵盐缓蚀剂的腐蚀速率减小近5倍。
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。

Claims (10)

1.一种α,β-不饱和酮类化合物，其特征在于，所述α,β-不饱和酮类化合物选自具有式I所示结构式的化合物、具有式II所示结构式的化合物中的至少一种；
Figure FDA0003594970600000011
在式I、式II中，Y1选自亚甲基、N、O、S中的任一种；Y2选自次甲基、N中的任一种；
R1选自C1-C24的烷基中的任一种；
R2选自氨基、羟基、＊-OSO3M、聚乙氧基醚基、取代的氨基、聚乙胺基、＊-NR3 +X1 -中的任一种；
M选自Na、K、Li中的任一种；
R3选自C1-C6的烷基、取代的C1-C6的烷基、C6-C12的芳基中的任一种；
X1选自卤素。
2.根据权利要求1所述的α,β-不饱和酮类化合物，其特征在于，所述取代的氨基中的取代基选自C6-C12的芳基中的任一种。
3.根据权利要求1所述的α,β-不饱和酮类化合物，其特征在于，所述聚乙氧基醚基中的乙氧基单元数为1～10；
所述聚乙胺基中的乙胺基单元数为1～10；
所述取代的C1-C6的烷基中的取代基选自C6-C12的芳基中的任一种。
4.权利要求1至3任一项所述的α,β-不饱和酮类化合物的制备方法，其特征在于，所述制备方法包括：
将含有化合物i和化合物ii的混合物，在碱性物存在下反应I，得到所述α,β-不饱和酮类化合物P；
所述α,β-不饱和酮类化合物P中的R2为羟基；
所述化合物i选自具有式III所示结构式的化合物、具有式IV所示结构式的化合物中的任一种；
Figure FDA0003594970600000021
所述化合物ii选自具有式V所示结构式的化合物中的任一种；
Figure FDA0003594970600000022
或者，
(a)将所述α,β-不饱和酮类化合物P与卤代试剂混合，反应II，得到卤代的中间产物K；
(b)将所述卤代的中间产物K与含有R2的亲核试剂反应III，即可得到所述α,β-不饱和酮类化合物O；
所述α,β-不饱和酮类化合物O中的R2选自氨基、*-OSO3M、聚乙氧基醚基、取代的氨基、聚乙胺基、*-NR3 +X1 -中的任一种；
或者，
将所述α,β-不饱和酮类化合物P与吡啶硫酸盐混合，反应IV，得到所述α,β-不饱和酮类化合物Q；
所述α,β-不饱和酮类化合物Q中的R2为*-OSO3M。
5.根据权利要求4所述的制备方法，其特征在于，所述反应I的条件为：反应温度为20℃～30℃；反应时间为18h～24h；
所述反应II的条件为：反应温度为10℃～20℃；反应时间为0.5h～4h；
所述反应III的条件为：反应温度为50℃～100℃；反应时间为0.5h～5h；
所述反应IV的条件为：反应温度为20℃～30℃；反应时间为0.5h～2h。
6.根据权利要求4所述的制备方法，其特征在于，在所述步骤(a)中，所述卤代试剂选自二氯亚砜、草酰氯、三氯氧磷、浓盐酸、三溴化磷中的至少一种；
所述含有R2的亲核试剂选自三乙胺、三丁胺、三苄胺、苯胺、二乙二醇、三甘醇、三丙二醇、三缩四乙二醇、五甘醇、八甘醇、N,N'-二(2-氨乙基)-1,3-丙二胺、二乙烯三胺、三乙烯四胺、1,8-二氨基-3,6-二氧杂辛烷中的至少一种。
7.根据权利要求4所述的制备方法，其特征在于，所述化合物i和所述化合物ii的摩尔比为0.5-1:1-10；
在所述步骤(a)中，所述α,β-不饱和酮类化合物P、卤代试剂和含有R2的亲核试剂的摩尔比为0.5-1:1-10:1-10；
所述α,β-不饱和酮类化合物P与吡啶硫酸盐的摩尔比为0.5-1:1-10。
8.根据权利要求4所述的制备方法，其特征在于，所述碱性物选自氢氧化钠、氢氧化钾、碳酸氢钠、碳酸钠、碳酸钾、碳酸铯、氢化钠、磷酸钾中的至少一种。
9.权利要求1至3任一项所述的α,β-不饱和酮类化合物、根据权利要求4至8任一项所述方法制备得到的α,β-不饱和酮类化合物中的至少一种在作为缓蚀剂中的应用。
10.根据权利要求9所述的应用，其特征在于，所述缓蚀剂用于碳钢防腐。
CN202210389352.5A 2022-01-26 2022-04-13 一种α,β-不饱和酮类化合物及其制备方法、应用 Active CN114656431B (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210093519 2022-01-26
CN2022100935193 2022-01-26

Publications (2)

Publication Number Publication Date
CN114656431A true CN114656431A (zh) 2022-06-24
CN114656431B CN114656431B (zh) 2023-11-28

Family

ID=82035370

Family Applications (2)

Application Number Title Priority Date Filing Date
CN202210389352.5A Active CN114656431B (zh) 2022-01-26 2022-04-13 一种α,β-不饱和酮类化合物及其制备方法、应用
CN202210674262.0A Active CN115057836B (zh) 2022-01-26 2022-06-14 一种酯类化合物及其制备方法、应用

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN202210674262.0A Active CN115057836B (zh) 2022-01-26 2022-06-14 一种酯类化合物及其制备方法、应用

Country Status (1)

Country Link
CN (2) CN114656431B (zh)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101535315A (zh) * 2006-10-13 2009-09-16 辉瑞有限公司 用作家畜动物的同化激素类药的杂环化合物
US20150232394A1 (en) * 2011-09-14 2015-08-20 Los Alamos National Security, Llc Compounds and methods for the production of long chain hydrocarbons from biological sources
CN109718850A (zh) * 2017-10-31 2019-05-07 中国科学院大连化学物理研究所 一种制备航空煤油前驱体的方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3852278A (en) * 1973-01-22 1974-12-03 Rohm & Haas Preparation of 4-(2-(furfurylideneamino)-phenyl)-3-thioallophanates
US20170226075A1 (en) * 2014-08-19 2017-08-10 Archer Daniels Midland Company Synthesis of Non-Ionic Surfactants From 5-Hydroxymethyl-2-Furfural, Furan-2,5-Dimethanol and Bis-2,5-Dihydroxymethyl-Tetrahydrofurans
CN106922145A (zh) * 2014-11-21 2017-07-04 阿彻丹尼尔斯米德兰德公司 5‑(羟甲基)‑糠醛还原产物的酸催化酰化

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101535315A (zh) * 2006-10-13 2009-09-16 辉瑞有限公司 用作家畜动物的同化激素类药的杂环化合物
US20150232394A1 (en) * 2011-09-14 2015-08-20 Los Alamos National Security, Llc Compounds and methods for the production of long chain hydrocarbons from biological sources
CN109718850A (zh) * 2017-10-31 2019-05-07 中国科学院大连化学物理研究所 一种制备航空煤油前驱体的方法

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
CACCHI, S. ET AL.: "A one-pot palladium-catalyzed synthesis of β,β-diaryl ketones and aldehydes from aryl iodides and α,β-unsaturated carbonyl compounds", 《SYNTHESIS》, no. 7, pages 575 *
CAS数据库: "RN：2307878-65-3", 《REGISTRY》, pages 1 *
GALKIN, KONSTANTIN I. ET AL.: "Towards Improved Biorefinery Technologies: 5-Methylfurfural as a Versatile C6 Platform for Biofuels Development", 《CHEMSUSCHEM》, vol. 12, no. 1, pages 185 - 189 *
W. W. FRENIEF ET AL.: "新型盐酸缓蚀剂α-链烯基苯酮", 《化学清洗》, pages 14 - 16 *
狄志刚等: "水性水喷砂防锈剂的研制及应用研究", 《涂料工业》, vol. 51, no. 12, pages 37 - 43 *
颜涛等: "一种β氨基酮缓蚀剂的合成及缓蚀性能", 《化工技术与开发》, vol. 47, no. 10, pages 5 - 8 *
颜肖慈等: "呋喃及其衍生物对铝缓蚀机理的量子化学研究", 《中国腐蚀与防护学报》, vol. 19, no. 6, pages 372 - 375 *

Also Published As

Publication number Publication date
CN115057836A (zh) 2022-09-16
CN114656431B (zh) 2023-11-28
CN115057836B (zh) 2023-11-28

Similar Documents

Publication Publication Date Title
CN108358760B (zh) 金属化物/钯化合物催化还原体系在脱苄基反应及氘代反应中的应用
CN114656431A (zh) 一种α,β-不饱和酮类化合物及其制备方法、应用
CN109797398B (zh) 一种二芳基碘盐类化合物作为金属缓蚀剂的应用
CN110590689B (zh) 一种具表面活性的缓蚀剂及其制备方法和应用
JP2020506160A (ja) アビバクタムの簡便な調製方法
JP6923520B2 (ja) 新規な５−アジド−５−デオキシ−２：３−イソプロピリデン−Ｄ−アラビノース化合物、それらの製造方法、およびＡｒａ−Ｎ３、Ｋｄｏ−Ｎ３および４ｅＫｄｏ−Ｎ３の合成のためのそれらの使用
AU2006209556B2 (en) Process for production of 5-chloro-2,4-dihydroxypyridine
JPS58213774A (ja) 新規アミノ配糖体
CN114456217A (zh) 一种烯糖化合物的合成方法
CN114671833B (zh) 一种呋喃双子季铵盐化合物及其制备方法和应用
JP4347488B2 (ja) 有機アジドの製造方法
CN100357294C (zh) 7－[2－(2－氨基噻唑－4－基)－2－羟基亚氨基乙酰胺－3－乙烯基－3－头孢烯－4－羧酸(顺式异构体)的新型晶体和其制备方法
CN1062268C (zh) 经sn2转化将醇转化成叠氮化物的方法
RU2778789C1 (ru) Способ получения s-никотина
JPS5936914B2 (ja) セフアロスポリン類縁体
JPS6072895A (ja) ２−ケトグロン酸およびそのエステルのケタ−ルの製造法
CN113861422B (zh) 含二茂钴阳离子侧基的聚硫醚缓蚀剂的制备方法及使用缓蚀剂体系
JPH058200B2 (zh)
JPS585199B2 (ja) 置換ペニシリン類の製造方法
JP7405991B2 (ja) ウリジン５’－二リン酸（ｕｄｐ）、その塩またはその水和物の製造方法
Kim et al. Synthesis and anion binding affinities of novel molecular tweezers based on chenodeoxycholic acid bearing different lengths of arm
SU1359340A1 (ru) Раствор дл травлени сталей
Boldron et al. Simple and efficient syntheses of 1, 10-phenanthrolines substituted at C3 or C3 and C8 by methoxy or hydroxy groups
JPH04187667A (ja) ２―置換ヒドロキシイミノプロパンジニトリルの製造法
CN116926557A (zh) 一种酰基硫脲类金属缓蚀剂及其制备方法与应用

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