CN114014767B - 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
CN114014767B
CN114014767B CN202111361903.9A CN202111361903A CN114014767B CN 114014767 B CN114014767 B CN 114014767B CN 202111361903 A CN202111361903 A CN 202111361903A CN 114014767 B CN114014767 B CN 114014767B
Authority
CN
China
Prior art keywords
compound
reaction
nitrogen
containing compound
atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111361903.9A
Other languages
Chinese (zh)
Other versions
CN114014767A (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

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 structural general formula of the nitrogen-containing compound is as follows

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, bohr's student Maria Goeppert-Mayer in her graduation paper, the primitive physical process of double quantum transition, proposed the possibility of absorbing Two photons simultaneously (i.e., two-photon absorption: two-Photon Absorption, hereinafter TPA). Two-photon absorption refers to the process of simultaneously absorbing two photons by one molecule under the action of strong laser, and is a phenomenon that light interacts with a substance under the action of strong laser. In a two-photon absorption process, the molecule absorbs the first photon to reach a virtual state that is not truly stable, but rather a combination of all possible states between the ground and excited states. Because the difference between the ground state and the excited state energy delta E is large, the virtual state can exist for a short time, which is only in the magnitude of femtoseconds, according to the Hessenberg inaccuracy principle. The two-photon absorption phenomenon was not observed in CaF 2:Eu2+ crystals by Kaiser and Garret first until 1961. When they pump CaF 2:Eu2+ crystals with a 694.3nm laser beam from a focused ruby laser, blue fluorescence, i.e. fluorescence up-converted, was observed, thus proving the existence of two-photon absorption phenomenon for the first time experimentally.
The photopolymerization process initiated by the occurrence of two-photon absorption is called two-photon polymerization. Two-photon polymerization micromachining is an important application of two-photon polymerization, which can be used to process some nano-scale microstructures for use as scaffolds for tissue engineering. The microstructure processed by two-photon polymerization has higher resolution, and can break through diffraction limit, so that the processed microstructure is finer and more complete. The efficiency of the two-photon initiator thus influences the effect of the polymerization and the applicable laser intensity and scanning speed. While the manufacturing resolution is almost directly determined.
However, current two-photon polymerization initiators remain relatively inefficient and insufficient for large-scale additive manufacturing. Therefore, the study of a high-efficiency two-photon polymerization initiator is extremely important.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in 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 structural formula shown in formula I:
Wherein X is selected from CR 1 2、C＝O、CR1＝CR1, O, or S, or is absent;
each Y is independently selected from N or CR 2;
Each R 2, each R 1 is independently selected from 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 may be cyclic 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 substituted group 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" means the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed compound, a crosslinked compound, a carbocyclic compound, or a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "number of ring atoms" described below, 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 heteroatom is preferably at least one selected from Si, N, P, O, S, ge, particularly preferably at least one selected from Si, N, P, O, 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 being 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 may also be interrupted by short non-aromatic units (< 10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, systems such as 9,9' -spirobifluorene, 9-diaryl fluorene, triarylamine, diaryl ether, and the like are likewise considered aromatic groups for the purposes of this invention.
Specifically, examples of the aromatic group are: benzene, biphenyl, naphthalene, anthracene, phenanthrene, benzophenanthrene, perylene, naphthacene, pyrene, benzopyrene, perylene, triphenylene, acenaphthene, fluorene, triphenylamine, triphenylphosphine oxide, tetraphenylsilicon, and derivatives thereof, preferably at least one of benzene, biphenyl, naphthalene, anthracene, phenanthrene, benzophenanthrene, pyrene, perylene, triphenylamine, triphenylphosphine oxide, and tetraphenylsilicon.
Specifically, examples of the heteroaromatic group 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, primary pyridine, quinazoline, quinazolinone, dibenzothiophene, spirofluorene, and derivatives thereof, preferably at least one of pyridine, pyrimidine, triazine, dibenzofuran, spirofluorene, 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 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 groups:
Wherein each W is independently selected from N, CR 5, c=o, and at least one W is N or c=o;
Each X 1 is independently selected from CR 6 2、C＝O、O、S、S＝O、S＝(O)2;
Each X 2 is independently selected from CR 7 2, O, S;
Each X 3 is independently selected from c= O, S = O, S = (O) 2;
Each R 3～R7 is independently selected from 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 two groups may be linked to each other to form a ring; wherein at least one R 3 is selected from 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 groups:
Wherein R 3、R4、R5、X1、X2 is defined as above, and m is selected from integers from 0 to 10.
In some embodiments of the invention, the nitrogen-containing compound has any one of the following structural formulas:
wherein X, Y, R, ar, R 3、R4、R5 and X 1 are as defined above.
In some embodiments of the invention, the nitrogen-containing compound has any one of the following structural formulas:
/>
/>
/>
In some embodiments of the invention, the solubility of the nitrogen-containing compound in toluene is greater than or equal to 0.05mg/ml, preferably greater than or equal to 2mg/ml, and most preferably greater than or equal to 5mg/ml at 25 ℃; at 25 ℃, the solubility of the nitrogen-containing compound in water is not less than 0.01mg/ml, preferably not less than 0.1mg/ml, most preferably not less than 1mg/ml.
In a second aspect, the present invention provides a process for the preparation of said nitrogen-containing compound, comprising the steps of, when R is present:
allowing compound 1-1A-B (OH) 2 to react with compound 1-2 Reaction to give compound 1-3/>Wherein M represents halogen;
halogen substitution is carried out on R in the compounds 1-3 to obtain the compounds 1-4
Allowing the compounds 1 to 4 to react with the compounds 1 to 5Reacting to obtain the nitrogen-containing compound
The group X, Y, R, ar, A is as previously described and R is present.
In some embodiments of the invention, the molar ratio of compound 1-1 to compound 1-2 is from 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, the reaction can be performed under the action of a catalyst which is commonly used in the field, and the catalyst can be palladium complex, such as Pd (PPh 3)4. In addition, the reaction between the compound 1-1 and the compound 1-2 is performed under alkaline condition, 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, the molar ratio of the alkaline substances to the compound 1-2 can be set to 3-5:1, and other ratios of alkaline substances can be selected according to practical situations, meanwhile, the solvent which is commonly used in the field can be selected according to practical situations, such as toluene, methylene dichloride, water, N-dimethyl formamide and N, N-dimethyl acetamide, and the mixture of any one or more of toluene, methylene dichloride, the compound 1-1 and the compound 1-2 can be preferably set to 1:20 mol ratio of toluene and the compound 1-2 can be set to 10 ml.
In some embodiments of the invention, the reaction temperature of compound 1-1 and compound 1-2 is 70 to 100 ℃, preferably 80 to 90 ℃, 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 halogen substitution may be performed by mixing the compounds 1-3 with an elemental halogen in a molar ratio of 0.9 to 1.2:1.
In some embodiments of the invention, the temperature of mixing the compounds 1-3 with elemental halogen is-10 to 10 ℃, preferably-5 to 0 ℃, more preferably about 0 ℃, in practice, the two may 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 ℃ for halogen substitution, and the time for the halogen substitution is 5-15 h. After the desired reaction time is reached, the reaction may be terminated by adding a sulfite solution to the reaction system.
In some embodiments of the invention, the molar ratio of compounds 1-4 to compounds 1-5 is from 0.8 to 1.2:1, preferably about 1:1. the reaction of compounds 1-4 with compounds 1-5 may be carried out under the catalytic action of palladium complexes [ e.g., pd (dba) 2、t-Bu3P、Pd(PPh3)4, etc. ] and/or alkoxides (e.g., naOBu-t), etc. In some preferred embodiments, the molar ratio of catalyst to compounds 1-4 is from 1 to 3:1, a step of; in some more preferred embodiments, the catalyst is a combination of Pd (dba) 2、t-Bu3 P and NaOBu-t, the molar ratio of Pd (dba) 2、t-Bu3 P to NaOBu-t being 1: (2-3): (150-250). Meanwhile, the solvent used for the reaction of the compounds 1 to 4 with the compounds 1 to 5 may be selected from the anhydrous organic solvents commonly used in the art, such as anhydrous toluene, etc., according to the actual situation.
In some embodiments of the invention, the reaction temperature of compounds 1-4 with compounds 1-5 is 80 to 100 ℃, preferably 85 to 95 ℃; the reaction time is 2-5 h.
Or when R exists, the preparation method of the nitrogen-containing compound comprises the following steps:
By reacting compound 2-1 With Compound 2-2/>Reaction to obtain compound 2-3/>Wherein M represents halogen;
halogen substitution is carried out on the compound 2-3 to obtain a compound 2-4
Reacting the compound 2-4 with the compound 2-5A-H to obtain a nitrogen-containing compound
The group X, Y, R, ar, A is 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 from 0.8 to 1.2:1, preferably about 1:1. the reaction of the compound 2-1 and the compound 2-2 can be carried out under the action of a catalyst used in the coupling reaction commonly used in the field, and the catalyst can be exemplified by palladium complex, such as Pd (PPh 3)4. In addition, the reaction of the compound 2-1 and the compound 2-2 is carried out under alkaline condition, 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, the molar ratio of the alkaline substances to the compound 2-2 can be set to 3-5:1, alkaline substances in other ratios can be selected according to actual conditions, meanwhile, solvents used in the reaction of the compound 2-1 and the compound 2-2 can be selected according to actual conditions, such as toluene, methylene dichloride, water, N-dimethylformamide and any mixture of any plurality of N, N-dimethylacetamide, the volume of the compound 2-1 and the compound 2-is preferably carried out in a mixed solvent of toluene and water, the ratio of the alkaline substances to the compound 2-2 can be set to 4:20 mol ratio of the compound 2-2 can be set to 1 ml.
In some embodiments of the invention, the reaction temperature of compound 2-1 and compound 2-2 is 70 to 100 ℃, preferably 80 to 90 ℃, 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 halogen substitution may be performed by mixing the compound 2-3 with an elemental halogen in a molar ratio of 2 to 2.5:1.
In some embodiments of the present invention, the mixing temperature of the compound 2-3 and the elemental halogen is-10 to 10 ℃, preferably-5 to 0 ℃, more preferably about 0 ℃, and in practice, the two may 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 ℃ for halogen substitution, and the time for the halogen substitution is 5-15 h. After the desired reaction time is reached, the reaction may be terminated by adding a sulfite solution to the reaction system.
In some embodiments of the invention, the molar ratio of compound 2-5 to compound 2-4 is from 2 to 5:1, preferably 4 to 5:1. the reaction of the compound 2-5 with the compound 2-4 may be performed under the catalytic action of a palladium complex [ e.g., palladium acetate, etc. ]. In some preferred embodiments, the ratio of catalyst to compound 2-4 is 150 to 250mg:1mmol. 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 triphenylphosphine), and the ratio of the organic reducing agent to the compound 2-4 is 0.5-1 g:1mmol. Preferably, an 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:1mmol.
In some embodiments of the invention, the reaction temperature of the compounds 2-5 and 2-4 is 100 to 150 ℃, preferably 100 to 120 ℃; the reaction time is 20-36 h.
Or when R is not present, the preparation method of the nitrogen-containing compound comprises the following steps:
allowing compound 3-1A-B (OH) 2 to react with compound 3-2 Reaction to give compound 3-3/>Wherein M represents halogen; /(I)
Allowing the compound 3-3 to react with the compound 3-4Reacting to obtain the nitrogen-containing compound
The group X, Y, ar, A is as previously described.
In some embodiments of the invention, the molar ratio of compound 3-1 to compound 3-2 is from 2 to 2.5:1, preferably about 2:1. in the actual operation, the reaction between the compound 3-1 and the compound 3-2 can be performed under the action of a catalyst used in the coupling reaction commonly used in the field, for example, palladium complexes such as Pd (PPh 3)4. In addition, the reaction between the compound 3-1 and the compound 3-2 is performed under alkaline conditions, in the 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, the molar ratio of the alkaline substances to the compound 3-2 can be set to 3-5:1, alkaline substances in other ratios can be selected according to the actual situation, simultaneously, solvents commonly used in the field can be selected according to the actual situation, for example, any one or more of toluene, methylene dichloride, water, N-dimethylformamide and N, N-dimethylacetamide can be selected, the volume of the mixed solvents of the compound 3-1 and the compound 3-2 is preferably performed in toluene and water can be set to 3-5:1, and the ratio of the solvent used in the reaction can be set to 1:4.
In some embodiments of the invention, the reaction temperature of compound 3-1 and compound 3-2 is 70 to 100 ℃, preferably 80 to 90 ℃, 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 from 0.8 to 1.2:1, preferably about 1:1. the reaction of the compound 3-3 with the compound 3-4 may be performed under the catalysis of palladium complexes [ e.g., pd (dba) 2、t-Bu3P、Pd(PPh3)4, etc. ] and/or alkoxides (e.g., naOBu-t), etc. In some preferred embodiments, the molar ratio of catalyst to compound 3-3 is from 1 to 3:1, a step of; in some more preferred embodiments, the catalyst is a combination of Pd (dba) 2、t-Bu3 P and NaOBu-t, the molar ratio of Pd (dba) 2、t-Bu3 P to NaOBu-t being 1: 2-3: 150 to 250. Meanwhile, the solvent used for the reaction of the compound 3-3 with the compound 3-4 may be selected from the anhydrous organic solvents commonly used in the art, such as anhydrous toluene, etc., according to the actual situation.
In some embodiments of the invention, the reaction temperature of compound 3-3 with 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 comprising the above nitrogen-containing compound as a raw material.
In some embodiments of the present invention, the raw materials of the composition further include a functional material, which may be flexibly selected according to the use, 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: 0.00001-100000.
When the polymer monomer material is contained, the nitrogen-containing compound may function as an initiator, and the weight percentage of the initiator relative to the polymer monomer material is 15wt% or less, preferably 12wt% or less, more preferably 9wt% or less, still more preferably 8wt% or less, and most preferably 7wt% or less.
The photosensitive resin material includes an acrylic resin and/or an acrylate resin.
The co-initiator comprises at least one of aliphatic tertiary amine, ethanolamines tertiary amine, tertiary amine benzoate and reactive amine.
The raw materials of the composition may further contain at least one solvent according to actual needs, and the solvent includes at least one of water and an organic solvent. The organic solvent comprises at least one of alcohols, aromatic, heteroaromatic, esters, aromatic ketones, aromatic ethers, aliphatic ketones, aliphatic ethers, alicyclic, alkanes, olefin solvents, wherein the ester solvents comprise at least one of carboxylic acid esters, boric acid esters, phosphate esters solvents; preferably comprising at least one of aromatic, heteroaromatic solvents.
Examples of aromatic or heteroaromatic solvents suitable for the present invention are, but not limited to: para-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluenes, 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-difluorodiphenyl methane, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenyl methane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α -dichlorodiphenyl methane, 4- (3-phenylpropyl) pyridine, benzyl benzoate, 1-bis (3, 4-dimethylphenyl) ethane, 2-isopropylnaphthalene, 2-quinolinecarboxylic acid, ethyl ester, 2-methylfuran, etc.;
Examples of aromatic ketone solvents suitable for the present invention are, but are 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-methylpropionophenone, 3-methylpropionophenone, 2-methylpropionophenone, and the like;
Examples of aromatic ether solvents suitable for the present invention are, but are not limited to: 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxane, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylphenyl ethyl ether, 1, 3-dipropoxybenzene, 1,2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidyl phenyl ether, dibenzyl ether, 4-t-butyl anisole, trans-p-propenyl anisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether.
Examples of aliphatic ketone solvents suitable for the present invention are, but not limited to: 2-nonene, 3-nonene, 5-nonene, 2-decanone, 2, 5-adipone, 2,6, 8-trimethyl-4-nonene, fenchyl ketone, 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 suitable carboxylate solvents for the present invention are, but are not limited to: octyl octanoate, decyl sebacate, alkyl stearate, alkyl benzoate, alkyl phenylacetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkyl lactone, alkyl oleate, 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-trichloroethane, 1, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydronaphthalene, decalin, indene and/or mixtures thereof.
The composition according to the invention, wherein the organic solvent is selected taking into account its boiling point parameters. In the invention, the boiling point of the organic solvent is more than or equal to 80 ℃; preferably not less than 130 ℃; more preferably not less than 150 ℃; and the most preferable temperature is more than or equal to 200 ℃.
A fourth aspect of the present invention is to provide a 3D printing ink, a raw material of which contains the composition.
The invention also provides application of the nitrogen-containing compound in preparing 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 the 3D printing ink through a 3D printing manufacturing technology.
The 3D printing fabrication techniques may be selected from, but are not limited to, photo-curing molding (Stereo lithography Apparatu, SLA), layered solid fabrication (Layered Solid Manufacturing, LOM), selective laser sintering molding (SELECTIVE LASER SINTERING, SLS), fused deposition molding (Fused Deposition Modeling, FDM), and Two-photon 3D printing (Two-photonpolymerization, TPP).
In some embodiments of the 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 section, can effectively improve the initiation efficiency of polymerization reaction, and overcomes the problems of low initiation efficiency of two-photon polymerization in the prior art.
Drawings
FIG. 1 is a chart showing the ultraviolet-visible light absorption spectrum and fluorescence spectrum of the compound A-2 of example 2.
Detailed Description
The technical scheme of the invention is further described below with reference to specific examples. The starting materials used in the examples below, unless otherwise specified, are all commercially available from conventional sources; the processes used, unless otherwise specified, are all conventional in the art.
Example 1
Synthesis of Compound A-1
(1) Synthesis of intermediate 3
Compound 1 (20.8 mmol), compound 2 (10.36 mmol), pd (PPh 3)4 (601 mg), sodium carbonate (34.72 mmol), toluene 200ml and water 70ml were added sequentially to a 500ml two port reaction flask, protected by N 2, reacted overnight at 85 ℃, the spot-on-plate reaction was completed, cooled to room temperature, the liquid separated, the aqueous phase was extracted twice with dichloromethane DCM.
(2) Synthesis of intermediate 4
Intermediate 3 (5 mmol) was dissolved in 100mL dichloromethane under ice bath, then 1.17mL dichloromethane solution of liquid bromine (5.3 mmol) was slowly added dropwise, after the dropwise addition was completed, the reaction was slowly returned to room temperature, stirring was continued overnight, the reaction was terminated by adding sodium sulfite aqueous solution, the organic phase was extracted with sodium carbonate aqueous solution and water several times, the organic phase was dried, and 1.88g intermediate 4 was obtained after column chromatography separation.
(3) Synthesis of Compound A-1
In a 1000ml two-port flask, intermediate 4 (0.1 mol), compound 5 (0.1 mol), pd (dba) 2(0.003mol),t-Bu3 P (0.009 mol), naOBu-t (0.2 mol), anhydrous toluene, and reaction at 90℃for 3 hours were placed. And (3) after-treatment, water washing, drying by anhydrous magnesium sulfate, and passing petroleum ether through a silica gel column to obtain the compound A-1 with the yield of 89%.
The characterization result of the nuclear magnetic resonance hydrogen spectrum and the mass spectrum of the compound A-1 is that ：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
(1) Synthesis of intermediate 7
Compound 6 (20 mmol), compound 2 (10 mmol), pd (PPh 3)4 (600 mg), sodium carbonate (35 mmol), toluene 200ml and water 70ml were added to a 500ml double port reaction flask, protected by N 2, reacted overnight at 85 ℃, the spot-on-plate reaction was completed, cooled to room temperature, the liquid separated, the aqueous phase extracted twice with DCM, the organic phases were combined, evaporated to dryness under reduced pressure, passed over a column of silica gel with DCM/pe=1/20 (v/v) over product, evaporated to dryness under reduced pressure to give 8.0g of intermediate 7.
(2) Synthesis of intermediate 8
Intermediate 7 (5 mmol) was dissolved in 100mL dichloromethane under ice bath, then 1.17mL dichloromethane solution of liquid bromine (5.3 mmol) was slowly added dropwise, after the dropwise addition was completed, the reaction was slowly returned to room temperature, stirring was continued overnight, the reaction was terminated by adding aqueous sodium sulfite solution, the organic phase was extracted with aqueous sodium carbonate solution and water several times, the organic phase was dried, and 3.8g intermediate 8 was obtained after column chromatography separation.
(3) Synthesis of Compound A-2
In a 1000ml two-port flask, intermediate 8 (0.1 mol), compound 9 (0.1 mol), pd (dba) 2(0.003mol),t-Bu3 P (0.009 mol), naOBu-t (0.2 mol), anhydrous toluene, and reaction at 90℃for 3 hours were placed. And (3) after-treatment, water washing, drying by anhydrous magnesium sulfate, and passing petroleum ether through a silica gel column to obtain the compound A-2 with the yield of 62%.
The characterization result of the nuclear magnetic resonance hydrogen spectrum and the mass spectrum of the compound A-2 is that ：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 fluorescence spectrum of the compound A-2 are shown in figure 1, and the spectrogram shows that the compound A-2 has ultraviolet-visible light absorption performance and fluorescence performance.
Example 3
Synthesis of Compound A-3
(1) Synthesis of intermediate 12
Compound 10 (20 mmol), compound 11 (20 mmol), pd (PPh 3)4 (600 mg), sodium carbonate (35 mmol), toluene 200ml and water 70ml were added to a 500ml double port reaction flask, protected by N 2, and reacted overnight at 85 ℃, the spot-on-plate reaction was completed, cooled to room temperature, the liquid separated, the aqueous phase was extracted twice with DCM, the organic phases were combined, evaporated to dryness under reduced pressure, passed over a column of silica gel with DCM/pe=1/20 (v/v) over the product, and evaporated to dryness under reduced pressure to give 5.7g of intermediate 12.
(2) Synthesis of intermediate 13
Intermediate 12 (2.5 mmol) was dissolved in 100mL dichloromethane under ice bath, then 1.17mL dichloromethane solution of liquid bromine (5.3 mmol) was slowly added dropwise, after the completion of the dropwise addition, the reaction was slowly returned to room temperature, stirring was continued overnight, the reaction was terminated by adding aqueous sodium sulfite solution, the organic phase was extracted several times with aqueous sodium carbonate solution and water, the organic phase was dried, and 1.2g intermediate 13 was obtained after column chromatography separation.
(3) Synthesis of Compound A-3
Intermediate 13 (0.3 mmol), compound 14 (1.3 mmol), palladium acetate 57mg and triphenylphosphine 0.205g were charged into a reactor, and after three times of nitrogen exchange by vacuum, 18mL of freshly distilled triethylamine was added and reacted at 110℃for 24 hours, and after the triethylamine was distilled off, the residual solid was purified by 1:4 (v: v) dichloromethane: petroleum ether is used as a developing agent for column chromatography to obtain a white solid compound A-3 with the yield of 43 percent.
The characterization result of the nuclear magnetic resonance hydrogen spectrum and the mass spectrum of the compound A-3 is that ：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
(1) Synthesis of intermediate 17
Compound 15 (20 mmol), compound 16 (10 mmol), pd (PPh 3)4 (600 mg), sodium carbonate (35 mmol), toluene 200ml and water 70ml were added to a 500ml double port reaction flask, protected by N 2, and reacted overnight at 85 ℃, the spot-on-plate reaction was completed, cooled to room temperature, the liquid separated, the aqueous phase was extracted twice with DCM, the organic phases were combined, evaporated to dryness under reduced pressure, passed over a column of silica gel with DCM/pe=1/20 (v/v) over the product, and evaporated to dryness under reduced pressure to give 3.5g of intermediate 17.
(2) Synthesis of Compound A-4
In a 1000ml two-port flask, compound 17 (0.1 mol), compound 18 (0.1 mol), pd (dba) 2(0.003mol),t-Bu3 P (0.009 mol), naOBu-t (0.2 mol), anhydrous toluene as a solvent, were added and reacted at 90℃for 3 hours. And (3) after-treatment, water washing, drying by anhydrous magnesium sulfate, and passing petroleum ether through a silica gel column to obtain the compound A-4 with the yield of 89%.
The characterization result of the nuclear magnetic resonance hydrogen spectrum and the mass spectrum of the compound A-4 is that ：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
In a glass vessel equipped with a stirrer, 900mg of the compound A-1 of example 1 (functioning as an initiator) and 90g of ethoxylated trimethylolpropane triacrylate (monomer) were placed under light-shielding conditions, and stirred and shaken for 24 hours to completely dissolve the compound A-1.
The compound A-1 was replaced by the equivalent mass of the compounds A-2, A-3, A-4 of examples 2 to 4, respectively, or by benzophenone BP(Comparative example 1), or M2CMK/>(Comparative example 2) different mixtures were obtained.
(1) Single photon polymerization efficiency
The testing method comprises the following steps: the prepared mixture is dripped on a clean glass sheet to prepare a film layer, the film layer is prebaked for 120s at 90 ℃, 365nm ultraviolet light is adopted for exposure, the exposure is 40mJ/cm 2, development is carried out for 50s at 23 ℃ (sodium hydroxide solution, OH - concentration is 0.5%), and the film is subjected to weight reduction test after baking for 20min at 230 ℃.
Weight reduction = (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.
The test results show that the nitrogen-containing compounds of examples 1 to 4, when used as initiators, have a lower weight loss than the conventional BP or M2CMK initiators, indicating that the amount of unpolymerized monomers is smaller and the photoinitiation effect is better.
(2) Two-photon polymerization efficiency
The testing method comprises the following steps: the prepared mixture is dripped on a clean glass sheet to prepare a film layer, the film layer is prebaked for 120s at 90 ℃, the film layer is exposed by femtosecond laser with the wavelength of 800nm and 80fs pulse femtosecond laser, developed for 50s at 23 ℃ (sodium hydroxide solution, OH - concentration is 0.5%), and the film layer is subjected to post-baking for 20min at 230 ℃, and the weight reduction test is carried out on the obtained film layer.
Weight reduction = (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 And (3) a photoinitiator: monomer (wt) Weight loss ratio (%)
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 the nitrogen-containing compounds of examples 1 to 4, when used as two-photon polymerization initiators, have a smaller weight loss ratio than the conventional initiator BP or M2CMK, indicating that the nitrogen-containing compounds have a smaller amount of unpolymerized monomers and have a better two-photon photoinitiation effect. Therefore, these nitrogen-containing compounds can be mixed with photosensitive resin materials, polymeric monomer materials, colorant materials, co-initiator materials, additive materials, crosslinkable polymer materials, organic dyes, etc. as needed to prepare compositions for certain uses, such as 3D printing inks, which are then processed to prepare various organic electronic devices and components thereof.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (4)

1. A composition characterized by: the raw materials of the composition contain a nitrogen-containing compound, and the chemical structure of the nitrogen-containing compound is any one of the following structural formulas:
the raw materials of the composition further comprise at least one of photosensitive resin materials, polymeric monomer materials, colorant materials, auxiliary initiator materials, additive materials, crosslinkable polymer materials and organic dyes.
2. A 3D printing ink, characterized in that: the raw material of the 3D printing ink contains the composition of claim 1.
3. An organic electronic device, characterized in that: a feedstock for preparing the organic electronic device comprising the composition of claim 1.
4. An organic electronic device, characterized in that: the feedstock for preparing the organic electronic device comprises components formed from the 3D printing ink of claim 2 via 3D printing fabrication techniques.
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 CN114014767A (en) 2022-02-08
CN114014767B true 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 (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007246790A (en) * 2006-03-17 2007-09-27 Ricoh Co Ltd Two-photon absorption material and its use
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

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7232913B2 (en) * 2004-09-28 2007-06-19 The Regents Of The University Of California Paracyclophane molecules for two-photon absorption applications
JP2008203573A (en) * 2007-02-20 2008-09-04 Fujifilm Corp Photosensitive composition and two-photon absorption optical recording medium

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007246790A (en) * 2006-03-17 2007-09-27 Ricoh Co Ltd Two-photon absorption material and its use
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
CN114014767A (en) 2022-02-08

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
JP5567889B2 (en) Anthracene derivative, compound using the same, composition, cured product, and method for producing the same
CN103130833B (en) Soluble oxime ester and aromatic ketone photo polymerization initiator
JP5778462B2 (en) Anthracene derivative and method for producing the same, curable composition, and cured product
Han et al. Functional isocoumarin-containing polymers synthesized by rhodium-catalyzed oxidative polycoupling of aryl diacid and internal diyne
CN108727517A (en) Fluorenes oxime ester lightlike initiating agent, preparation method and application containing polymerizable groups
CN102212150A (en) Polymerizable thioxanthone photoinitiator containing auxiliary initiator amine and preparation method thereof
CN109970696B (en) Coumarin oxime ester photoinitiator
CN114014767B (en) Nitrogen-containing compound and preparation method and application thereof
CN100528852C (en) Piperazine-based sensitisers
CN109134712B (en) Fluorene multifunctionality photoinitiator, preparation method and application thereof
TW201927914A (en) Yellow compound, coloring composition containing the compound, coloring agent for color filter and color filter wherein the yellow compound has excellent solubility in an organic solvent
CN101942046A (en) Benzophenone fragment and p-nitrodiphenylethene fragment-containing tree like visible light photoinitiator and synthesis and application thereof
CN101225240A (en) Conjugated benzophenone-containing triphenylamine dyes as well as synthesis and uses thereof
CN110066352A (en) Oxime ester lightlike initiating agent, preparation method, photosensitive polymer combination and application
CN101654399B (en) Phenanthrene benzene derivative and polymer thereof, copolymer containing phenanthrene benzene derivative and luminous material composition
KR20240005843A (en) Oxime ester photoinitiator with chalcone structure and manufacturing method and application thereof
CN100580026C (en) P-nitro diphenyl ethylene dye containing diphenyl ketone via ether bond linkage as well as synthesis and application
KR101723872B1 (en) Bisisobenzofurandionylantracene compound, preparation method thereof and organic insulationg layer using the same
CN103980392A (en) Star-like visible light initiator having conjugated structure and containing benzophenone fragments as well as synthesis and application of visible light initiator
CN103145888A (en) Visible light initiator with different benzophenone fragment branch numbers and conjugated structure
TWI394770B (en) Copolymers containing phenyl-phenanthrene derivative and light-emitting material compositions
CN101643518A (en) Squaric acid dye/hexaarylbiimidazole complex capable of being used for visible photosensitive system
CN114478500B (en) Coumarin two-photon initiator and synthesis method and application 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