CN114014767A - Nitrogen-containing compound and preparation method and application thereof - Google Patents

Nitrogen-containing compound and preparation method and application thereof Download PDF

Info

Publication number
CN114014767A
CN114014767A CN202111361903.9A CN202111361903A CN114014767A CN 114014767 A CN114014767 A CN 114014767A CN 202111361903 A CN202111361903 A CN 202111361903A CN 114014767 A CN114014767 A CN 114014767A
Authority
CN
China
Prior art keywords
substituted
unsubstituted
atoms
compound
nitrogen
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
CN202111361903.9A
Other languages
Chinese (zh)
Other versions
CN114014767B (en
Inventor
温华文
侯慧玉
张焱琴
车璇
黄榆慧
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.)
Guangzhou Institute of Technology
Original Assignee
Guangzhou Institute of Technology
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 Guangzhou Institute of Technology filed Critical Guangzhou Institute of Technology
Priority to CN202111361903.9A priority Critical patent/CN114014767B/en
Publication of CN114014767A publication Critical patent/CN114014767A/en
Application granted granted Critical
Publication of CN114014767B publication Critical patent/CN114014767B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
    • C07D335/12—Thioxanthenes
    • C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
    • C07D335/16—Oxygen atoms, e.g. thioxanthones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/22—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/24—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/58—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton
    • 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
    • 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
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/46—Oxygen atoms
    • C07D213/50—Ketonic radicals
    • 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
    • C07D213/60—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/14—Thiadiazoles; Hydrogenated thiadiazoles condensed with carbocyclic rings or ring systems
    • 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
    • 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
    • C07D333/26—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/30—Hetero atoms other than halogen
    • C07D333/36—Nitrogen atoms
    • 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
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks
    • 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
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/93—Spiro compounds
    • C07C2603/94—Spiro compounds containing "free" spiro atoms

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Civil Engineering (AREA)
  • Composite Materials (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a nitrogen-containing compound, a preparation method and application thereof, wherein the nitrogen-containing compound has a structural general formula

Description

Nitrogen-containing compound and preparation method and application thereof
Technical Field
The invention relates to the technical field of two-photon materials, in particular to a nitrogen-containing compound and a preparation method and application thereof.
Background
In 1931, Boer's student Maria Goeppert-Mayer proposed the possibility of absorbing Two photons simultaneously (i.e., Two-Photon Absorption: Two-Photon Absorption, hereinafter TPA) in her graduation paper "elementary physical Process of Two-Photon transition". Two-photon absorption refers to a process in which one molecule absorbs two photons simultaneously under the action of strong laser, which is a phenomenon in which light interacts with a substance under the action of strong laser. In the two-photon absorption process, the molecule absorbs the first photon to a virtual state, which is not a truly stable state, but rather a combination of all possible states between the ground state and the excited state. Because the energy delta E difference between the ground state and the excited state is large, the virtual state can exist for a short time only in the order of femtosecond according to the heisenberg inaccurate measurement principle. Until 1961, Kaiser followed Garret first in CaF2:Eu2+Two-photon absorption phenomenon was observed in the crystal. When they pump CaF with a focused 694.3nm laser beam from a ruby laser2:Eu2+Upon crystallization, blue fluorescence, i.e., fluorescence converted in energy, was observed, thereby experimentally confirming the presence of the two-photon absorption phenomenon for the first time.
The photopolymerization process due to the occurrence of two-photon absorption is called two-photon polymerization. Two-photon polymerization micromachining is an important application of two-photon polymerization, and can be used for machining some nano-scale microstructures to be used as tissue engineering scaffolds. The microstructure processed by two-photon polymerization has higher resolution, can break through the diffraction limit, and enables the processed microstructure to be more detailed and complete. The efficiency of the two-photon initiator thus affects the effect of the polymerization as well as the applicable laser intensity and scanning speed. While almost directly determining the fabrication resolution.
However, current two-photon polymerization initiators are still relatively inefficient and insufficient for large scale additive manufacturing. Therefore, the research of the efficient two-photon polymerization initiator is very important.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a nitrogen-containing compound which can effectively improve the initiation efficiency of two-photon polymerization reaction.
Meanwhile, the invention also provides a preparation method and application of the nitrogen-containing compound.
Specifically, the invention adopts the following technical scheme:
in a first aspect of the present invention, there is provided a nitrogen-containing compound having the formula shown in formula I below:
Figure BDA0003359247530000021
wherein X is selected from CR1 2、C＝O、CR1＝CR1O or S, or absent;
each Y is independently selected from N or CR2；
Each R2Each R1Independently of one another, from the group consisting of H, halogen, nitro, cyano, isocyano, aldehyde, substituted or unsubstituted carbonyl having 2 to 10C atoms, substituted or unsubstituted ester having 1 to 10C atoms, substituted or unsubstituted isocyanate having 1 to 10C atoms, substituted or unsubstituted alkyl having 2 to 10C atomsSubstituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl having 2 to 10C atoms, substituted or unsubstituted aromatic group having 5 to 61 ring atoms, substituted or unsubstituted heteroaromatic group having 5 to 61 ring atoms, and adjacent groups may form a ring with each other;
r is selected from a substituted or unsubstituted carbonyl group having 1 to 10C atoms, a substituted or unsubstituted ester group having 1 to 10C atoms, a substituted or unsubstituted isocyanate group having 1 to 10C atoms, a substituted or unsubstituted alkyl group having 1 to 10C atoms, a substituted or unsubstituted alkenyl group having 2 to 10C atoms, a substituted or unsubstituted alkynyl group having 2 to 10C atoms, a substituted or unsubstituted aromatic group having 5 to 61 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 61 ring atoms, or is absent;
each Ar is independently selected from a substituted or unsubstituted aromatic group having 5 to 61 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 61 ring atoms, a substituted or unsubstituted alkenyl group having 2 to 10C atoms, an alkynyl group having 2 to 10C atoms;
each a is independently selected from a substituted or unsubstituted aromatic group having 5 to 61 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 61 ring atoms, and at least one a is a chemical structure having electron withdrawing properties.
In the present invention, "substituted" means that a hydrogen atom in a substituent is substituted by a substituent.
Adjacent groups refer to adjacent groups, i.e., groups separated by one to two atoms.
The "number of ring atoms" represents the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, and a heterocyclic compound) in which atoms are bonded in a ring shape. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The "number of ring atoms" described below is the same unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.
An aromatic group refers to a hydrocarbon group containing at least one aromatic ring, including monocyclic groups and polycyclic ring systems. Heteroaromatic groups refer to hydrocarbon groups (containing heteroatoms) that contain at least one heteroaromatic ring, including monocyclic groups and polycyclic ring systems. The hetero atom is preferably at least one member selected from the group consisting of Si, N, P, O, S and Ge, and particularly preferably at least one member selected from the group consisting of Si, N, P, O and S. These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, i.e., form a fused ring. At least one of these rings of the polycyclic ring is aromatic or heteroaromatic. For the purposes of the present invention, aromatic or heteroaromatic groups include not only aromatic or heteroaromatic systems, but also systems in which a plurality of aromatic or heteroaromatic groups are interrupted by short nonaromatic units (< 10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, for example, systems such as 9,9' -spirobifluorene, 9, 9-diarylfluorene, triarylamines, diaryl ethers, etc., are also considered aromatic groups for the purposes of this invention.
Specifically, examples of the aromatic group are: benzene, biphenyl, naphthalene, anthracene, phenanthrene, triphenylene, perylene, tetracene, pyrene, benzopyrene, perylene, triphenylene, acenaphthene, fluorene, triphenylamine, triphenylphosphoroxide, tetraphenylsilicon, and derivatives thereof, preferably at least one of benzene, biphenyl, naphthalene, anthracene, phenanthrene, triphenylene, pyrene, perylene, triphenylamine, triphenylphosphoroxide, and tetraphenylsilicon.
Specifically, examples of heteroaromatic groups are: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, phthalazine, quinoxaline, phenanthridine, primadine, quinazoline, quinazolinone, dibenzothiophene, silafluorene, spirofluorene, spirosilafluorene, and derivatives thereof, preferably at least one of pyridine, pyrimidine, triazine, dibenzothiophene, silafluorene, spirofluorene, spirosilafluorene, carbazole, thiophene, furan, thiazole, oxadiazole.
The nitrogen-containing compound according to the first aspect of the present invention has at least the following advantageous effects:
the nitrogen-containing compound has a polycyclic structure, has a good two-photon absorption cross section, and can effectively improve the initiation efficiency of two-photon polymerization reaction.
In some embodiments of the invention, each a is independently selected from any one of the following:
Figure BDA0003359247530000041
wherein each W is independently selected from N, CR5C ═ O, and at least one W is N or C ═ O;
each X1Independently of one another from CR6 2、C＝O、O、S、S＝O、S＝(O)2；
Each X2Independently of one another from CR7 2、O、S；
Each X3Independently of one another, from C O, S O, S (O)2；
Each R3～R7Independently of one another, from the group consisting of H, halogen, nitro, cyano, isocyano, aldehyde, substituted or unsubstituted carbonyl having 2 to 10C atoms, substituted or unsubstituted ester having 1 to 10C atoms, substituted or unsubstituted isocyanate having 1 to 10C atoms, substituted or unsubstituted alkyl having 1 to 10C atoms, substituted or unsubstituted alkenyl having 2 to 10C atoms, substituted or unsubstituted alkynyl having 2 to 10C atoms, substituted or unsubstituted aromatic having 5 to 61 ring atoms, substituted or unsubstituted heteroaromatic having 5 to 61 ring atoms, and two adjacent groups can be joined to one another to form a ring; wherein at least one R is3Selected from the group consisting of halogen, nitro, cyano, isocyano, aldehyde, substituted or unsubstituted carbonyl having 2 to 10C atoms;
each n independently represents an integer of 0 to 10.
In some embodiments of the invention, each a is independently selected from any one of the following:
Figure BDA0003359247530000051
wherein R is3、R4、R5、X1、X2Wherein m is an integer of 0 to 10.
In some embodiments of the invention, the nitrogen-containing compound has any one of the following structural formulas:
Figure BDA0003359247530000052
Figure BDA0003359247530000061
Figure BDA0003359247530000071
wherein, X, Y, R, Ar, R3、R4、R5And X1As defined above.
In some embodiments of the invention, the nitrogen-containing compound has any one of the following structural formulas:
Figure BDA0003359247530000081
Figure BDA0003359247530000091
Figure BDA0003359247530000101
Figure BDA0003359247530000111
Figure BDA0003359247530000121
Figure BDA0003359247530000131
Figure BDA0003359247530000141
in some embodiments of the invention, the nitrogen-containing compound has a solubility in toluene of 0.05mg/ml or more, preferably 2mg/ml or more, and most preferably 5mg/ml or more, at 25 ℃; the nitrogen-containing compound has a solubility in water of 0.01mg/ml or more, preferably 0.1mg/ml or more, and most preferably 1mg/ml or more at 25 ℃.
The second aspect of the present invention is to provide a process for producing the nitrogen-containing compound, when R is present, comprising the steps of:
reacting a compound 1-1A-B (OH)2With the compounds 1-2
Figure BDA0003359247530000151
Reacting to obtain compound 1-3
Figure BDA0003359247530000152
Wherein M represents halogen;
performing halogen substitution on R in the compounds 1-3 to obtain compounds 1-4
Figure BDA0003359247530000153
Reacting said compounds 1-4 with compounds 1-5
Figure BDA0003359247530000154
Reacting to obtain a nitrogen-containing compoundCompound (I)
Figure BDA0003359247530000155
The groups X, Y, R, Ar, A are as previously described, and R is present.
In some embodiments of the present invention, the molar ratio of compound 1-1 to compound 1-2 is 2 to 2.5: 1, preferably about 2: 1. the reaction between the compound 1-1 and the compound 1-2 is a cross-coupling reaction, and can be carried out during the reaction under the action of a catalyst for coupling reaction commonly used in the art, and the catalyst can be exemplified by a palladium complex such as Pd (PPh)3)4. In actual operation, the reaction of the compound 1-1 and the compound 1-2 is carried out under alkaline conditions, alkaline reaction conditions can be formed by adding alkaline substances such as sodium carbonate, sodium hydroxide, potassium carbonate and potassium hydroxide into a reaction system, and the molar ratio of the alkaline substances to the compound 1-2 can be set to be 3-5: 1, other proportions of alkaline substances can be selected according to actual conditions. Meanwhile, the solvent used for the reaction of the compound 1-1 and the compound 1-2 can be any one or a mixture of any more of toluene, dichloromethane, water, N-dimethylformamide and N, N-dimethylacetamide according to the actual conditions. The compound 1-1 and the compound 1-2 are preferably reacted in a mixed solvent of toluene and water, and the volume ratio of the toluene to the water can be set to be 2-4: 1; the ratio of the reactant to the solvent can be set according to the actual situation, for example, the ratio of the solvent to the compound 1-1 can be set to 10-20 mL: 1 mmol.
In some embodiments of the present invention, the reaction temperature of the compound 1-1 and the compound 1-2 is 70 to 100 ℃, preferably 80 to 90 ℃, and more preferably about 85 ℃. The reaction time is 5-15 h. The reaction is carried out under an inert protective atmosphere.
In some embodiments of the present invention, halogen substitution may be performed by mixing the compound 1-3 with an elemental halogen, and the molar ratio of the elemental halogen to the compound 1-3 is 0.9 to 1.2: 1.
in some embodiments of the present invention, the compound 1-3 and the halogen are mixed at a temperature of-10 to 10 ℃, preferably-5 to 0 ℃, and more preferably about 0 ℃, and in practical operation, the two can be mixed under ice bath conditions. After the compound 1-3 and the halogen simple substance are mixed, the temperature is raised to 0-40 ℃, preferably 20-30 ℃, and halogen substitution is carried out, wherein the halogen substitution time is 5-15 h. After the desired reaction time is reached, the reaction can be terminated by adding a sulfite solution to the reaction system.
In some embodiments of the invention, the molar ratio of compound 1-4 to compound 1-5 is 0.8 to 1.2: 1, preferably about 1: 1. the reaction of the compounds 1-4 with the compounds 1-5 can be carried out in the presence of a palladium complex [ e.g., Pd (dba)2、t-Bu3P、Pd(PPh3)4Etc. of]And/or alkoxides (e.g., NaOBu-t), and the like. In some preferred embodiments, the molar ratio of the catalyst to the compounds 1-4 is 1-3: 1; in some more preferred embodiments, the catalyst is Pd (dba)2、t-Bu3A combination of P and NaOBu-t, said Pd (dba)2、t-Bu3The molar ratio of P to NaOBu-t is 1: (2-3): (150-250). Meanwhile, the solvent used for the reaction of the compounds 1-4 and 1-5 can be selected from anhydrous organic solvents commonly used in the art, such as anhydrous toluene and the like, according to actual conditions.
In some embodiments of the present invention, the reaction temperature of the compound 1-4 and the compound 1-5 is 80 to 100 ℃, preferably 85 to 95 ℃; the reaction time is 2-5 h.
Or, when R is present, the preparation method of the nitrogen-containing compound comprises the following steps:
reacting the compound 2-1
Figure BDA0003359247530000171
With the compound 2-2
Figure BDA0003359247530000172
Reacting to obtain a compound 2-3
Figure BDA0003359247530000173
Wherein M represents halogen;
performing halogen substitution on the compound 2-3 to obtain a compound 2-4
Figure BDA0003359247530000174
Reacting the compound 2-4 with a compound 2-5A-H to obtain a nitrogen-containing compound
Figure BDA0003359247530000175
The groups X, Y, R, Ar, A are as previously described, and R is present.
In some embodiments of the invention, the molar ratio of compound 2-1 to compound 2-2 is 0.8 to 1.2: 1, preferably about 1: 1. the reaction of the compound 2-1 with the compound 2-2 can be carried out by a catalyst for coupling reaction commonly used in the art, and the catalyst can be exemplified by a palladium complex such as Pd (PPh)3)4. In actual operation, alkaline reaction conditions can be formed by adding alkaline substances such as sodium carbonate, sodium hydroxide, potassium carbonate and potassium hydroxide into a reaction system, and the molar ratio of the alkaline substances to the compound 2-2 can be set to be 3-5: 1, other proportions of alkaline substances can be selected according to actual conditions. Meanwhile, the solvent used for the reaction of the compound 2-1 and the compound 2-2 can be any one or a mixture of any more of toluene, dichloromethane, water, N-dimethylformamide and N, N-dimethylacetamide according to the actual conditions. The compound 2-1 and the compound 2-2 are preferably reacted in a mixed solvent of toluene and water, and the volume ratio of the toluene to the water can be set to be 2-4: 1; the ratio of the reactant to the solvent can be set according to the actual situation, for example, the ratio of the solvent to the compound 2-1 can be set to 10-20 ml: 1 mmol.
In some embodiments of the present invention, the reaction temperature of the compound 2-1 and the compound 2-2 is 70 to 100 ℃, preferably 80 to 90 ℃, and more preferably about 85 ℃. The reaction time is 5-15 h. The reaction is carried out under an inert protective atmosphere.
In some embodiments of the present invention, halogen substitution may be performed by mixing the compound 2-3 with an elemental halogen, and the molar ratio of the elemental halogen to the compound 2-3 is 2 to 2.5: 1.
in some embodiments of the present invention, the compound 2-3 and the halogen are mixed at a temperature of-10 to 10 ℃, preferably-5 to 0 ℃, and more preferably about 0 ℃, and in practical operation, the two can be mixed under ice bath conditions. After the compound 2-3 and the halogen simple substance are mixed, the temperature is raised to 0-40 ℃, preferably 20-30 ℃, and halogen substitution is carried out, wherein the halogen substitution time is 5-15 h. After the desired reaction time is reached, the reaction can be terminated by adding a sulfite solution to the reaction system.
In some embodiments of the present invention, the molar ratio of compound 2-5 to compound 2-4 is 2-5: 1, preferably 4 to 5: 1. the reaction process of the compounds 2-5 and 2-4 can be carried out under the catalysis of palladium complexes [ such as palladium acetate and the like ]. In some preferred embodiments, the ratio of the catalyst to compounds 2-4 is from 150 to 250 mg: 1 mmol. Preferably, the reaction process of the compound 2-5 and the compound 2-4 is carried out under the action of an organic reducing agent (such as trimethylphenylphosphine), and the ratio of the organic reducing agent to the compound 2-4 is 0.5-1 g: 1 mmol. Preferably, organic amine (such as triethylamine) can be added into the reaction system of the compound 2-5 and the compound 2-4, and the ratio of the organic amine to the compound 2-4 is 50-80 ml: 1 mmol.
In some embodiments of the present invention, the reaction temperature of the compound 2-5 and the compound 2-4 is 100 to 150 ℃, preferably 100 to 120 ℃; the reaction time is 20-36 h.
Alternatively, when R is absent, the process for preparing the nitrogen-containing compound comprises the steps of:
reacting a compound 3-1A-B (OH)2With the compound 3-2
Figure BDA0003359247530000181
Reacting to obtain a compound 3-3
Figure BDA0003359247530000182
Wherein M represents halogen;
reacting said compound 3-3 with said compound 3-4
Figure BDA0003359247530000191
Reacting to obtain a nitrogen-containing compound
Figure BDA0003359247530000192
The groups X, Y, Ar and A are as described above.
In some embodiments of the present invention, the molar ratio of compound 3-1 to compound 3-2 is 2 to 2.5: 1, preferably about 2: 1. the reaction between the compound 3-1 and the compound 3-2 can be carried out by using a catalyst for coupling reaction commonly used in the art, and as an example, a palladium complex such as Pd (PPh) can be used3)4. In actual operation, alkaline reaction conditions can be formed by adding alkaline substances such as sodium carbonate, sodium hydroxide, potassium carbonate and potassium hydroxide into a reaction system, and the molar ratio of the alkaline substances to the compound 3-2 can be set to be 3-5: 1, other proportions of alkaline substances can be selected according to actual conditions. Meanwhile, the solvent used for the reaction of the compound 3-1 and the compound 3-2 can be any one or a mixture of any more of toluene, dichloromethane, water, N-dimethylformamide and N, N-dimethylacetamide according to the actual conditions. The compound 3-1 and the compound 3-2 are preferably reacted in a mixed solvent of toluene and water, and the volume ratio of the toluene to the water can be set to be 2-4: 1; the ratio of the reactant to the solvent can be set according to the actual situation, for example, the ratio of the solvent to the compound 3-1 can be set to 10-20 ml: 1 mmol.
In some embodiments of the present invention, the reaction temperature of the compound 3-1 and the compound 3-2 is 70 to 100 ℃, preferably 80 to 90 ℃, and more preferably about 85 ℃. The reaction time is 5-15 h. The reaction is carried out under an inert protective atmosphere.
In some embodiments of the invention, the molar ratio of compound 3-3 to compound 3-4 is 0.8 to 1.2: 1, preferably about 1: 1. the reaction of the compound 3-3 with the compound 3-4 may be carried out in the presence of a palladium complex [ e.g., Pd (dba)2、t-Bu3P、Pd(PPh3)4Etc. of]And/or alkoxides (e.g., NaOBu-t), and the like. In some preferred embodiments, the molar ratio of the catalyst to compound 3-3 is 1 to 3: 1; in some more preferred embodiments, the catalyst is Pd (dba)2、t-Bu3A combination of P and NaOBu-t, said Pd (dba)2、t-Bu3The molar ratio of P to NaOBu-t is 1: 2-3: 150 to 250. Meanwhile, the solvent used for the reaction of the compound 3-3 and the compound 3-4 can be an anhydrous organic solvent commonly used in the art, such as anhydrous toluene and the like, according to practical situations.
In some embodiments of the present invention, the reaction temperature of the compound 3-3 and the compound 3-4 is 80 to 100 ℃, preferably 85 to 95 ℃; the reaction time is 2-5 h.
In a third aspect of the present invention, there is provided a composition wherein the raw material contains the above-mentioned nitrogen-containing compound.
In some embodiments of the present invention, the raw materials of the composition further comprise a functional material, which can be flexibly selected according to the application, for example, at least one of a photosensitive resin material, a polymeric monomer material, a colorant material, a co-initiator material, an additive material, a crosslinkable polymer material, and an organic dye. The ratio of the nitrogen-containing compound to the functional material may be set according to the actual situation, for example, the molar ratio of the nitrogen-containing compound to the functional material is set to 1: 0.00001 to 100000.
When a polymeric monomer material is present, the nitrogen-containing compound can function as an initiator, preferably at most 15 wt%, more preferably at most 12 wt%, even more preferably at most 9 wt%, even more preferably at most 8 wt%, and most preferably at most 7 wt% of the polymeric monomer material.
The photosensitive resin material includes an acrylic resin and/or an acrylate resin.
The co-initiator comprises at least one of aliphatic tertiary amine, ethanolamine tertiary amine, tertiary amine benzoate and active amine.
According to actual needs, the raw materials of the composition can also contain at least one solvent, and the solvent comprises at least one of water and an organic solvent. The organic solvent comprises at least one of alcohols, aromatic, heteroaromatic, ester, aromatic ketone, aromatic ether, aliphatic ketone, aliphatic ether, alicyclic, alkane and olefin solvents, wherein the ester solvent comprises at least one of carboxylic ester, boric ester and phosphate ester solvents; preferably at least one of aromatic, heteroaromatic solvents is included.
Examples of aromatic or heteroaromatic solvents suitable for the present invention are, but not limited to: p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3, 4-tetramethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, cyclohexylbenzene, benzylbutylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2, 4-trichlorobenzene, 4-difluorodiphenylmethane, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α -dichlorodiphenylmethane, 4- (3-phenylpropyl) pyridine, benzyl benzoate, 1-bis (3, 4-dimethylphenyl) ethane, 2-isopropylnaphthalene, quinoline, isoquinoline, methyl 2-furancarboxylate, ethyl 2-furancarboxylate, and the like;
examples of aromatic ketone solvents suitable for the present invention are, but not limited to: 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, and the like;
examples of aromatic ether solvents suitable for the present invention are, but not limited to: 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethylacetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxan, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylphenyl ether, 1, 3-dipropoxybenzene, 1,2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidylphenyl ether, dibenzyl ether, 4-t-butylanisole, trans-p-propenylanisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, methyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether.
Examples of aliphatic ketone solvents suitable for the present invention are, but not limited to: 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2, 5-hexanedione, 2,6, 8-trimethyl-4-nonanone, fenchone, phorone, isophorone, di-n-amyl ketone, and the like; or aliphatic ethers such as amyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and the like.
Examples of carboxylate solvents suitable for the present invention are, but not limited to: alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, etc., with octyl octanoate, diethyl sebacate, diallyl phthalate, isononyl isononanoate being particularly preferred.
The solvents listed above may be used alone or as a mixture of two or more organic solvents.
In certain preferred embodiments, a composition according to the present invention comprises a nitrogen-containing compound or mixture as described above and at least one organic solvent, and may further comprise another organic solvent, examples of which include, but are not limited to: methanol, ethanol, 2-methoxyethanol, methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1, 4-dioxane, acetone, methyl ethyl ketone, 1, 2-dichloroethane, 3-phenoxytoluene, 1,1, 1-trichloroethane, 1,1,2, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene, decalin, indene, and/or mixtures thereof.
The compositions according to the invention, in which the organic solvent is selected taking into account its boiling point parameter. In the invention, the boiling point of the organic solvent is more than or equal to 80 ℃; preferably equal to or more than 130 ℃; more preferably not less than 150 ℃; most preferably greater than or equal to 200 ℃.
In a fourth aspect of the present invention, there is provided a 3D printing ink, wherein the raw material of the 3D printing ink contains the composition.
The invention also provides application of the nitrogen-containing compound in manufacturing fluorescent materials or photocuring materials.
The invention also provides an organic electronic device, wherein the raw material for preparing the organic electronic device contains the nitrogen-containing compound, or the raw material for preparing the organic electronic device contains the composition, or the organic electronic device contains an element formed by 3D printing manufacturing technology of the 3D printing ink.
The 3D printing Manufacturing technology can be selected from, but not limited to, stereolithography apparatus (SLA), Layered Solid fabrication (LOM), Selective Laser Sintering (SLS), Fused Deposition Modeling (FDM), and Two-photon 3D printing (TPP).
In some embodiments of the present invention, the Organic electronic device comprises at least one of an Organic Light Emitting Diode (OLED), an Organic photovoltaic cell (OPV), an Organic light Emitting cell (OLEEC), an Organic Field Effect Transistor (OFET), an Organic light Emitting field effect transistor, an Organic laser, an Organic spintronic device, an optical information storage device, an Organic sensor, an Organic Plasmon Emitting Diode (Organic Plasmon Emitting Diode).
Compared with the prior art, the invention has the following beneficial effects:
the nitrogen-containing compound has a good two-photon absorption cross section, can effectively improve the initiation efficiency of polymerization reaction, and solves the problems of low initiation efficiency of two-photon polymerization and the like in the prior art.
Drawings
FIG. 1 is a graph showing an ultraviolet-visible light absorption spectrum and a fluorescence spectrum of Compound A-2 of example 2.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples. The starting materials used in the following examples, unless otherwise specified, are available from conventional commercial sources; the processes used, unless otherwise specified, are conventional in the art.
Example 1
Synthesis of Compound A-1
Figure BDA0003359247530000231
(1) Synthesis of intermediate 3
Compound 1(20.8mmol), Compound 2(10.36mmol), Pd (PPh) were sequentially added3)4(601mg), sodium carbonate (34.72mmol), toluene 200ml and water 70ml were charged into a 500ml two-necked flask, N2Protected and reacted at 85 ℃ overnight. After the reaction, the plate was cooled to room temperature, separated, and the aqueous phase was extracted twice with dichloromethane, DCM. The organic phases were combined, evaporated to dryness under reduced pressure, passed through a column with silica gel, passed through a DCM/PE (petroleum ether) ═ 1/20(v/v) product, evaporated to dryness under reduced pressure to give 6.7g of intermediate 3.
(2) Synthesis of intermediate 4
Dissolving the intermediate 3(5mmol) in 100mL of dichloromethane in ice bath, slowly dropwise adding 1.17mL of dichloromethane solution of liquid bromine (5.3mmol), slowly returning to room temperature after dropwise adding, continuously stirring for reacting overnight, adding sodium sulfite aqueous solution to terminate the reaction, extracting the organic phase for multiple times by using sodium carbonate aqueous solution and water, drying the organic phase, and performing column chromatography to obtain 1.88g of intermediate 4.
(3) Synthesis of Compound A-1
Adding into a 1000ml two-mouth bottleIntermediate 4(0.1mol), Compound 5(0.1mol), Pd (dba)2(0.003mol)，t-Bu3P (0.009mol), NaOBu-t (0.2mol), dry toluene, at 90 ℃ for 3 hours. The product was washed with water, dried over anhydrous magnesium sulfate, and passed through a silica gel column with petroleum ether to obtain Compound A-1 in a yield of 89%.
The characterization results of the nuclear magnetic resonance hydrogen spectrum and the mass spectrum of the compound A-1 are as follows:1H NMR(300MHz,CDCl3):δ9.06(2H,s),8.61(2H,d),8.42(2H,d),8.10(1H,s),7.80–7.12(20H,m))；ESI-MS(m/z):610(M+H)+.Elemental analyses(C,H,N)Anal.Calc.for C41H27N4OS:C,80.76；H,4.46；N,6.89,Found:C,81.03；H,4.42；N,6.97。
example 2
Synthesis of Compound A-2
Figure BDA0003359247530000241
(1) Synthesis of intermediate 7
Compound 6(20mmol), compound 2(10mmol), Pd (PPh) were sequentially added3)4(600mg), sodium carbonate (35mmol), toluene (200 ml) and water (70 ml) were charged into a 500ml two-necked reaction flask, N2Protected and reacted at 85 ℃ overnight. After the reaction, the plate was cooled to room temperature, separated, and the aqueous phase was extracted twice with DCM. The organic phases were combined, evaporated to dryness under reduced pressure, chromatographed on silica gel, passed over DCM/PE (1/20) (v/v) and evaporated to dryness under reduced pressure to give 8.0g of intermediate 7.
(2) Synthesis of intermediate 8
Dissolving the intermediate 7(5mmol) in 100mL of dichloromethane in ice bath, slowly dropwise adding 1.17mL of dichloromethane solution of liquid bromine (5.3mmol), slowly returning to room temperature after dropwise adding, continuously stirring for reacting overnight, adding sodium sulfite aqueous solution to terminate the reaction, extracting the organic phase for multiple times by using sodium carbonate aqueous solution and water, drying the organic phase, and performing column chromatography to obtain 3.8g of intermediate 8.
(3) Synthesis of Compound A-2
A1000 ml two-necked flask was charged with intermediate 8(0.1mol), Compound 9(0.1mol), Pd (dba)2(0.003mol)，t-Bu3P (0.009mol), NaOBu-t (0.2mol), dry toluene, at 90 ℃ for 3 hours. The product was washed with water, dried over anhydrous magnesium sulfate, and passed through a silica gel column with petroleum ether to obtain Compound A-2 in a yield of 62%.
The characterization results of the nuclear magnetic resonance hydrogen spectrum and the mass spectrum of the compound A-2 are as follows:1H NMR(300MHz,CDCl3):δ8.52(1H,s),8.13(4H,m),7.90–7.48(22H,m),7.37(6H,m),2.65-3.00(4H,m),1.92-2.23(4H,m),1.30(32H,m),0.53(12H,m))；ESI-MS(m/z):1141(M+H)+.Elemental analyses(C,H,N)Anal.Calc.for C83H85N3O:C,87.40；H,7.51；N,3.68,Found:C,87.43；H,7.50；N,3.65。
the ultraviolet-visible absorption spectrum and the fluorescence spectrum of the compound A-2 are shown in figure 1, and the spectrogram shows that the compound A-2 has ultraviolet-visible absorption performance and fluorescence performance.
Example 3
Synthesis of Compound A-3
Figure BDA0003359247530000251
(1) Synthesis of intermediate 12
Compound 10(20mmol), compound 11(20mmol), Pd (PPh) were sequentially added3)4(600mg), sodium carbonate (35mmol), toluene (200 ml) and water (70 ml) were charged into a 500ml two-necked reaction flask, N2Protected and reacted at 85 ℃ overnight. After the reaction, the plate was cooled to room temperature, separated, and the aqueous phase was extracted twice with DCM. The organic phases were combined, evaporated to dryness under reduced pressure, passed through a column with silica gel, passed through DCM/PE-1/20 (v/v) and evaporated to dryness under reduced pressure to give 5.7g of intermediate 12.
(2) Synthesis of intermediate 13
Dissolving the intermediate 12(2.5mmol) in 100mL of dichloromethane in ice bath, slowly dropwise adding 1.17mL of dichloromethane solution of liquid bromine (5.3mmol), slowly returning to room temperature after dropwise adding, continuously stirring for reacting overnight, adding sodium sulfite aqueous solution to terminate the reaction, extracting the organic phase with sodium carbonate aqueous solution and water for multiple times, drying the organic phase, and performing column chromatography to obtain 1.2g of intermediate 13.
(3) Synthesis of Compound A-3
Adding the intermediate 13(0.3mmol), the compound 14(1.3mmol), 57mg of palladium acetate and 0.205g of trimethylphosphine into a reactor, vacuumizing and changing nitrogen for three times, adding 18mL of freshly distilled triethylamine, reacting at 110 ℃ for 24 hours, and after distilling off the triethylamine, reacting the residual solid with a reaction solution of 1: 4 (v: v) dichloromethane: and (3) performing column chromatography by using petroleum ether as a developing agent to obtain a white solid compound A-3 with the yield of 43%.
The characterization results of the nuclear magnetic resonance hydrogen spectrum and the mass spectrum of the compound A-3 are as follows:1H NMR(300MHz,CDCl3):δ8.55(1H,s),8.30-8.28(4H,m),8.05-7.75(8H,m),7.55(2H,d),7.37(2H,d),7.22–7.13(6H,m),5.01(4H,m),3.34(4H,m),1.50-1.30(8H,m),0.60(6H,m))；ESI-MS(m/z):836(M+H)+.Elemental analyses(C,H,N)Anal.Calc.for C54H45NO4S2:C,77.58；H,5.43；N,1.68,Found:C,77.53；H,5.43；N,1.68。
example 4
Synthesis of Compound A-4
Figure BDA0003359247530000261
(1) Synthesis of intermediate 17
Compound 15(20mmol), compound 16(10mmol), Pd (PPh) were sequentially added3)4(600mg), sodium carbonate (35mmol), toluene (200 ml) and water (70 ml) were charged into a 500ml two-necked reaction flask, N2Protected and reacted at 85 ℃ overnight. After the reaction, the plate was cooled to room temperature, separated, and the aqueous phase was extracted twice with DCM. The organic phases were combined, evaporated to dryness under reduced pressure, chromatographed on silica gel, passed over DCM/PE 1/20(v/v) and evaporated to dryness under reduced pressure to give 3.5g of intermediate 17.
(2) Synthesis of Compound A-4
In a 1000ml two-necked flask was added compound 17(0.1mol), compound 18(0.1mol), Pd (dba)2(0.003mol)，t-Bu3P (0.009mol), NaOBu-t (0.2mol), dry toluene as solvent, at 90 ℃ for 3 hours. The product was washed with water, dried over anhydrous magnesium sulfate, and passed through a silica gel column with petroleum ether to obtain Compound A-4 in a yield of 89%.
The characterization results of the nuclear magnetic resonance hydrogen spectrum and the mass spectrum of the compound A-4 are as follows:1H NMR(300MHz,CDCl3):δ8.32-8.27(4H,m),8.05(2H,d),7.85-7.80(3H,m),7.57-7.30(10H,m),7.00(2H,m),4.45(4H,m),1.75-1.45(8H,m),0.61(6H,m))；ESI-MS(m/z):674(M+H)+.Elemental analyses(C,H,N)Anal.Calc.for C44H39N3O4:C,78.43；H,5.83；N,6.24,Found:C,78.50；H,5.81；N,6.24。
example 5
900mg of Compound A-1 (functioning as an initiator) from example 1 and 90g of ethoxylated trimethylolpropane triacrylate (monomer) were added to a glass vessel equipped with a stirrer under exclusion of light, and the mixture was stirred and shaken for 24 hours to completely dissolve Compound A-1.
The compound A-1 is respectively replaced by the compounds A-2, A-3 and A-4 of the examples 2-4 with equal mass, or replaced by benzophenone BP
Figure BDA0003359247530000271
(comparative example 1), or M2CMK
Figure BDA0003359247530000272
(comparative example 2), different mixtures were obtained.
(1) Single photon polymerization efficiency
The test method comprises the following steps: dropping the prepared mixture on a clean glass sheet to obtain a film layer, baking at 90 deg.C for 120s, exposing with 365nm ultraviolet light at exposure of 40mJ/cm2Development for 50s at 23 ℃ (sodium hydroxide solution, OH)-Concentration of 0.5%), post-baking at 230 ℃ for 20min, and carrying out weight loss test on the obtained film.
Weight loss (weight of film and glass sheet after first drying-weight of film and glass sheet after second drying)/weight of film and glass sheet after first drying.
The results are shown in Table 1.
Table 1.
Figure BDA0003359247530000273
Figure BDA0003359247530000281
The test results show that when the nitrogen-containing compounds of examples 1-4 are used as initiators, the weight reduction rate is smaller than that of a commonly used initiator BP or M2CMK, which indicates that the amount of unpolymerized monomers is less and the photoinitiation effect is better.
(2) Two-photon polymerization efficiency
The test method comprises the following steps: dropping the prepared mixture on clean glass sheet to obtain film, prebaking at 90 deg.C for 120s, exposing with 800nm femtosecond laser and 80fs pulsed femtosecond laser, and developing at 23 deg.C for 50s (sodium hydroxide solution, OH)-Concentration of 0.5%), post-baking at 230 ℃ for 20min, and carrying out weight loss test on the obtained film.
Weight loss (weight of film and glass sheet after first drying-weight of film and glass sheet after second drying)/weight of film and glass sheet after first drying.
The results are shown in Table 2.
Table 2.
Photoinitiator Photoinitiator (2): monomer (wt) Weight loss (%)
Example 1 A-1 1：100 1.4
Example 2 A-2 1：100 2.1
Example 3 A-3 1：100 1.5
Example 4 A-4 1：100 1.5
Comparative example 1 BP 1：100 98.0
Comparative example 2 M2CMK 1：100 4.3
The test results show that when the nitrogen-containing compounds of examples 1 to 4 are used as two-photon polymerization initiators, the weight reduction rate is smaller than that of a commonly used initiator BP or M2CMK, which indicates that the amount of unpolymerized monomers is less and the two-photon photoinitiation effect is better. Therefore, these nitrogen-containing compounds can be mixed with photosensitive resin materials, polymeric monomer materials, colorant materials, initiator aid materials, additive materials, crosslinkable polymer materials, organic dyes, etc. as required to prepare compositions for certain applications, such as 3D printing inks, and then processed to prepare various organic electronic devices and components thereof.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A nitrogen-containing compound having the general structural formula shown in the following formula (I):
Figure FDA0003359247520000011
wherein X is selected from CR1 2、C＝O、CR1＝CR1O or S, or absent;
each Y is independently selected from N or CR2；
Each R2Each R1Independently of one another, from the group consisting of H, halogen, nitro, cyano, isocyano, aldehyde, substituted or unsubstituted carbonyl having 2 to 10C atoms, substituted or unsubstituted ester having 1 to 10C atoms, substituted or unsubstituted isocyanate having 1 to 10C atoms, substituted or unsubstituted alkyl having 1 to 10C atoms, substituted or unsubstituted alkenyl having 2 to 10C atoms, substituted or unsubstituted alkynyl having 2 to 10C atoms, substituted or unsubstituted aromatic having 5 to 61 ring atoms, substituted or unsubstituted heteroaromatic having 5 to 61 ring atoms, and adjacent groups can form a ring with one another;
r is selected from a substituted or unsubstituted carbonyl group having 1 to 10C atoms, a substituted or unsubstituted ester group having 1 to 10C atoms, a substituted or unsubstituted isocyanate group having 1 to 10C atoms, a substituted or unsubstituted alkyl group having 1 to 10C atoms, a substituted or unsubstituted alkenyl group having 2 to 10C atoms, a substituted or unsubstituted alkynyl group having 2 to 10C atoms, a substituted or unsubstituted aromatic group having 5 to 61 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 61 ring atoms, or is absent;
each Ar is independently selected from a substituted or unsubstituted aromatic group having 5 to 61 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 61 ring atoms, a substituted or unsubstituted alkenyl, alkynyl; each a is independently selected from a substituted or unsubstituted aromatic group having 5 to 61 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 61 ring atoms, and at least one a is a chemical structure having electron withdrawing properties.
2. The nitrogen-containing compound according to claim 1, wherein: each A is independently selected from any one of the following groups:
Figure FDA0003359247520000021
Figure FDA0003359247520000031
wherein each W is independently selected from N, CR5C ═ O, and at least one W is N or C ═ O;
each X1Independently of one another from CR6 2、C＝O、O、S、S＝O、S＝(O)2；
Each X2Independently of one another from CR7 2、O、S；
Each X3Independently of one another, from C O, S O, S (O)2；
Each R3～R7Independently of one another, from the group consisting of H, halogen, nitro, cyano, isocyano, aldehyde, substituted or unsubstituted carbonyl having 2 to 10C atoms, substituted or unsubstituted ester having 1 to 10C atoms, substituted or unsubstituted isocyanate having 1 to 10C atoms, substituted or unsubstituted alkyl having 1 to 10C atoms, substituted or unsubstituted alkenyl having 2 to 10C atoms, aldehyde, or aldehyde, or a substituted or unsubstituted ester group, or substituted or unsubstituted isocyanate, or substituted or unsubstituted alkyl having 1 to which is substituted or unsubstituted alkyl, or substituted or unsubstituted alkyl having 1 to 10C atoms, or substituted or 10C atoms, or substituted or 10,A substituted or unsubstituted alkynyl group having 2 to 10C atoms, a substituted or unsubstituted aromatic group having 5 to 61 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 61 ring atoms, and two adjacent groups may be connected to each other to form a ring; wherein at least one R is3Selected from the group consisting of halogen, nitro, cyano, isocyano, aldehyde, substituted or unsubstituted carbonyl having 2 to 10C atoms;
each n independently represents an integer of 0 to 10.
3. The nitrogen-containing compound according to claim 2, wherein: each A is independently selected from any one of the following groups:
Figure FDA0003359247520000041
wherein R is3、R4、R5、X1、X2The definition of (A) is as defined in claim 2, and m is an integer of 0 to 10.
4. The nitrogen-containing compound according to any one of claims 1 to 3, wherein: the nitrogen-containing compound has any one of the following structural formulas:
Figure FDA0003359247520000051
Figure FDA0003359247520000061
Figure FDA0003359247520000071
Figure FDA0003359247520000081
Figure FDA0003359247520000091
Figure FDA0003359247520000101
Figure FDA0003359247520000111
5. a process for producing a nitrogen-containing compound according to any one of claims 1 to 4, characterized in that:
when R is present, the preparation method comprises the following steps:
reacting a compound 1-1A-B (OH)2With the compounds 1-2
Figure FDA0003359247520000121
Reacting to obtain compound 1-3
Figure FDA0003359247520000122
Wherein M represents halogen;
performing halogen substitution on R in the compounds 1-3 to obtain compounds 1-4
Figure FDA0003359247520000123
Reacting said compounds 1-4 with compounds 1-5
Figure FDA0003359247520000124
Reacting to obtain a nitrogen-containing compound
Figure FDA0003359247520000125
Alternatively, the preparation method of the nitrogen-containing compound comprises the following steps:
reacting the compound 2-1
Figure FDA0003359247520000131
With the compound 2-2
Figure FDA0003359247520000132
Reacting to obtain a compound 2-3
Figure FDA0003359247520000133
Wherein M represents halogen;
performing halogen substitution on the compound 2-3 to obtain a compound 2-4
Figure FDA0003359247520000134
Reacting the compound 2-4 with a compound 2-5A-H to obtain a nitrogen-containing compound
Figure FDA0003359247520000141
The groups X, Y, R, Ar, A are as defined in any one of claims 1 to 4;
when R is not existed, the preparation method of the nitrogen-containing compound comprises the following steps:
reacting a compound 3-1A-B (OH)2With the compound 3-2
Figure FDA0003359247520000142
Reacting to obtain a compound 3-3
Figure FDA0003359247520000143
Wherein M represents halogen;
reacting said compound 3-3 with said compound 3-4
Figure FDA0003359247520000144
Reacting to obtain a nitrogen-containing compound
Figure FDA0003359247520000145
The groups X, Y, Ar, A are as defined in any one of claims 1 to 4.
6. A composition characterized by: the composition comprises the nitrogen-containing compound according to any one of claims 1 to 4 as a raw material.
7. The composition of claim 6, wherein: the raw materials of the composition also comprise functional materials, and the functional materials comprise at least one of photosensitive resin materials, polymerized monomer materials, colorant materials, initiator aid materials, additive materials, crosslinkable high polymer materials and organic dyes.
8. A 3D printing ink, characterized in that: the raw material for the 3D printing ink contains the composition according to claim 6 or 7.
9. Use of the nitrogen-containing compound according to any one of claims 1 to 4 for producing a fluorescent material or a photocurable material.
10. An organic electronic device, characterized by: a raw material for preparing the organic electronic device contains the nitrogen-containing compound as defined in any one of claims 1 to 4, or a raw material for preparing the organic electronic device contains the composition as defined in claim 6 or 7, or an element formed by 3D printing manufacturing technology of the 3D printing ink as defined in claim 8.
CN202111361903.9A 2021-11-17 2021-11-17 Nitrogen-containing compound and preparation method and application thereof Active CN114014767B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111361903.9A CN114014767B (en) 2021-11-17 2021-11-17 Nitrogen-containing compound and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111361903.9A CN114014767B (en) 2021-11-17 2021-11-17 Nitrogen-containing compound and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114014767A true CN114014767A (en) 2022-02-08
CN114014767B CN114014767B (en) 2024-04-30

Family

ID=80064676

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111361903.9A Active CN114014767B (en) 2021-11-17 2021-11-17 Nitrogen-containing compound and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114014767B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060208235A1 (en) * 2004-09-28 2006-09-21 Bazan Guillermo C Paracyclophane molecules for two-photon absorption applications
JP2007246790A (en) * 2006-03-17 2007-09-27 Ricoh Co Ltd Two-photon absorption material and its use
US20080199811A1 (en) * 2007-02-20 2008-08-21 Fujifilm Corporation Photosensitive composition and two-photon absorption photorecording medium
CN111484468A (en) * 2019-01-25 2020-08-04 烟台显华光电材料研究院有限公司 Compound for preparing organic photoelectric device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060208235A1 (en) * 2004-09-28 2006-09-21 Bazan Guillermo C Paracyclophane molecules for two-photon absorption applications
JP2007246790A (en) * 2006-03-17 2007-09-27 Ricoh Co Ltd Two-photon absorption material and its use
US20080199811A1 (en) * 2007-02-20 2008-08-21 Fujifilm Corporation Photosensitive composition and two-photon absorption photorecording medium
CN111484468A (en) * 2019-01-25 2020-08-04 烟台显华光电材料研究院有限公司 Compound for preparing organic photoelectric device

Also Published As

Publication number Publication date
CN114014767B (en) 2024-04-30

Similar Documents

Publication Publication Date Title
JP6833171B2 (en) Fluorene photoinitiators, methods for producing them, photocurable compositions having them, and use of fluorene photoinitiators in the field of photocuring.
KR101567837B1 (en) Photoinitiators with fluorene structure and reactive liquid crystal compositions, and photoresist compositions comprising the same
CN108148055B (en) D-pi-A type organic fluorescent material based on naphthalene and preparation method thereof
CN109776419B (en) Pyrazoline group-containing sulfonium salt and preparation method and application thereof
CN103130833B (en) Soluble oxime ester and aromatic ketone photo polymerization initiator
Han et al. Functional isocoumarin-containing polymers synthesized by rhodium-catalyzed oxidative polycoupling of aryl diacid and internal diyne
WO2011049021A1 (en) Anthracene derivative, compound obtained therefrom, composition, cured object, and process for producing same
CN109232668B (en) Ferrocene derivative used as photo-oxidation-reduction catalyst in photopolymerization and composition thereof
CN114014767B (en) Nitrogen-containing compound and preparation method and application thereof
CN109134712B (en) Fluorene multifunctionality photoinitiator, preparation method and application thereof
CN101225240A (en) Conjugated benzophenone-containing triphenylamine dyes as well as synthesis and uses thereof
KR20240005843A (en) Oxime ester photoinitiator with chalcone structure and manufacturing method and application thereof
CN110066352A (en) Oxime ester lightlike initiating agent, preparation method, photosensitive polymer combination and application
CN101942046A (en) Benzophenone fragment and p-nitrodiphenylethene fragment-containing tree like visible light photoinitiator and synthesis and application thereof
KR101723872B1 (en) Bisisobenzofurandionylantracene compound, preparation method thereof and organic insulationg layer using the same
CN100580026C (en) P-nitro diphenyl ethylene dye containing diphenyl ketone via ether bond linkage as well as synthesis and application
CN108467390B (en) Thiophene dimethylketoxime acetate containing biscarbazole as photoinitiator, preparation method and application thereof
CN103980392A (en) Star-like visible light initiator having conjugated structure and containing benzophenone fragments as well as synthesis and application of visible light initiator
Tsuchimura et al. Novel acid amplifier generating disulfonimide as superacid
CN101643518A (en) Squaric acid dye/hexaarylbiimidazole complex capable of being used for visible photosensitive system
JP2018118935A (en) Novel compound, photoacid generator containing the compound, and photosensitive resin composition containing the photoacid generator
CN114478500B (en) Coumarin two-photon initiator and synthesis method and application thereof
CN103145888A (en) Visible light initiator with different benzophenone fragment branch numbers and conjugated structure
CN113292585B (en) BODIPY-benzothiadiazole-porphyrin-carbazole quaternary system linear compound and preparation method thereof
CN109369614B (en) Indene [2,1-a ] fluorene thiophene macrocyclic material and synthetic method thereof

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