CN114195729B - Benzotriazine single free radical compound and preparation method thereof - Google Patents

Benzotriazine single free radical compound and preparation method thereof Download PDF

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CN114195729B
CN114195729B CN202111587846.6A CN202111587846A CN114195729B CN 114195729 B CN114195729 B CN 114195729B CN 202111587846 A CN202111587846 A CN 202111587846A CN 114195729 B CN114195729 B CN 114195729B
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benzotriazine
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CN114195729A (en
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胡晓光
刘旭影
李华清
王鲜
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Zhengzhou University
Guangdong Electronic Information Engineering Research Institute of UESTC
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    • C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
    • C07D253/08—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 condensed with carbocyclic rings or ring systems
    • C07D253/10—Condensed 1,2,4-triazines; Hydrogenated condensed 1,2,4-triazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
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    • 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
    • C07D409/04—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 directly linked by a ring-member-to-ring-member bond
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Abstract

The invention belongs to the technical field of novel organic magnetic materials, and particularly relates to a benzotriazine single free radical compound and a preparation method thereof. The method introduces Ar-H ⋯ pi-rich into the 1,2, 4-benzotriazine free radicalAIEThe gene group is prepared into a benzotriazine single free radical compound. The benzotriazine single-free radical compound prepared by the invention has high spin performance and can be used for preparing magnetic materials or electronic devices.

Description

Benzotriazine single free radical compound and preparation method thereof
Technical Field
The invention relates to the technical field of novel organic magnetic materials, in particular to a benzotriazine single free radical compound and a preparation method thereof.
Background
The potential use of highly spin organic free genes in organic magnets and spintronics has gained increasing attention. In general, high spin diradicals and multi-radicals are readily available through strong ferromagnetic coupling interactions within the molecule. The design and preparation of high spin Shan Ziyou groups is challenging, which requires efficient intermolecular spin interactions and ordered packing, however, which is difficult to regulate and predict. One way to obtain high spin molecules, which have low stability and tend to form diamagnetic sigma dimers, is to build planar conjugated radicals, where shorter intermolecular distances can cause strong pi-pi interactions and efficient orbital overlap. However, various molecular design strategies are difficult to extend to other functional groups and radical systems. Therefore, it is important to find a strategy with universality to obtain high spin Shan Ziyou groups.
Disclosure of Invention
Aiming at the problems and the defects existing in the prior art, the invention aims to provide a benzotriazine single free radical compound and a preparation method thereof.
In order to achieve the aim of the invention, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a benzotriazine single radical compound, the structural formula of which is shown as formula 1:
Figure BDA0003428640890000011
wherein R is selected from any one of formula A, formula B, formula C, formula D, formula E, formula F, formula H and formula I;
Figure BDA0003428640890000021
the second aspect of the invention provides a preparation method of the benzotriazine single radical compound in the first aspect, which comprises the following steps:
s1: adding the compound A and the compound B into the solvent A, dissolving to obtain a mixed solution, adding triethylamine into the mixed solution, heating and refluxing for reaction for 12-36 h at the temperature of 85-90 ℃, cooling the reaction solution to room temperature after the reaction is finished, filtering, collecting filtrate, and removing the solvent in the filtrate to obtain an intermediate product; wherein the structural formula of the compound A is selected from any one of a formula a, a formula b, a formula c, a formula d, a formula e, a formula f, a formula h and a formula i;
Figure BDA0003428640890000022
the structural formula of the compound B is shown as a formula 2;
Figure BDA0003428640890000023
s2: and (3) dissolving the intermediate product obtained in the step (S1) in a solvent B, adding 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) and palladium carbon powder (the specification of the palladium carbon powder is 10 wt%) into the solvent B, stirring the mixture for reaction in an aerobic environment, filtering and collecting filtrate after the reaction is finished, removing the solvent in the filtrate to obtain a solid, and separating and purifying the solid to obtain the benzotriazine single free radical compound shown in the structural formula (1).
According to the preparation method, preferably, the specific operation of separation and purification is as follows: dissolving the solid by using a solvent B, and separating by using a chromatographic column after dissolving; the chromatographic column is a neutral silica gel chromatographic column treated by triethylamine.
According to the above preparation method, preferably, in step S1, the molar ratio of compound a to compound B is 1:1.25, and the molar ratio of triethylamine to compound a is 3:1; in the step S2, the molar ratio of the 1, 8-diazabicyclo [5.4.0] undec-7-ene to the compound A was 2:1, and the mass ratio of the palladium carbon powder (specification of the palladium carbon powder was 10wt%) to the compound A was 1:50.
According to the above preparation method, preferably, the solvent a is tetrahydrofuran; the solvent B is dichloromethane.
According to the above preparation method, preferably, the preparation method of the compound a represented by the structural formula a, formula d or formula f is as follows: compound C and pinacol phenylborate and tetrakis (triphenylphosphine) palladium (Pd [ P (C) 6 H 5 ) 3 ] 4 ) Adding the mixture into the solvent C, and then adding a potassium carbonate solution to obtain a mixture; heating the mixture to 85-90 ℃ in the atmosphere of protective gas, and carrying out heating reflux reaction for 12-36 h; extracting the reaction liquid by using an organic solvent D after the reaction is finished, collecting an organic solvent layer, evaporating the organic solvent layer to dryness to obtain a solid, and separating and purifying the solid to obtain a compound A;
wherein the structural formula of the compound C is selected from any one of a formula a-1, a formula d-1 and a formula f-1;
Figure BDA0003428640890000031
according to the above preparation method, preferably, the molar ratio of compound C, pinacol phenylborate to tetrakis (triphenylphosphine) palladium is 1: (1.5-4.5): 0.05; the molar ratio of potassium carbonate to compound C in the mixture was 7:1.
According to the above preparation method, preferably, the solvent C is tetrahydrofuran, and the organic solvent D is dichloromethane.
According to the above preparation method, preferably, the preparation method of the compound C represented by the structural formula d-1 or formula f-1 is as follows: compound D and 4-aminophenylboronic acid pinacol ester and tetrakis (triphenylphosphine) palladium (Pd [ P (C) 6 H 5 ) 3 ] 4 ) Adding the mixture into the solvent E, and then adding a potassium carbonate solution to obtain a mixture; heating the mixture to 85-90 ℃ in the atmosphere of protective gas, and carrying out heating reflux reaction for 12-36 h; extracting the reaction liquid by using an organic solvent F after the reaction is finished, collecting an organic solvent layer, evaporating the organic solvent layer to dryness to obtain a solid, and separating and purifying the solid to obtain a compound C;
wherein the structural formula of the compound D is shown as a formula D-2 or a formula f-2;
Figure BDA0003428640890000041
according to the above preparation method, preferably, the molar ratio of the compound D, 4-aminophenylboronic acid pinacol ester to tetrakis (triphenylphosphine) palladium is 1:1:0.05; the solvent E is tetrahydrofuran, and the organic solvent F is dichloromethane.
According to the above preparation method, preferably, the preparation method of the compound a having the structural formula shown in formula b or formula e is: compound E and 4-aminophenylboronic acid pinacol ester and tetrakis (triphenylphosphine) palladium (Pd [ P (C) 6 H 5 ) 3 ] 4 ) Adding the mixture into the solvent G, and then adding a potassium carbonate solution to obtain a mixture; heating the mixture to 85-90 ℃ in the atmosphere of protective gas, and carrying out heating reflux reaction for 12-36 h; extracting the reaction liquid by using an organic solvent H after the reaction is finished, collecting an organic solvent layer, evaporating the organic solvent layer to dryness to obtain a solid, and separating and purifying the solid to obtain a compound A; wherein the structural formula of the compound E is shown as a formula b-1 or a formula E-1; the compound E shown in the structural formula b-1 has a substance name of 3-Bromo-2-phenylthiopene (cas No. 38071-53-3); a compound E of the formula E-1The material name is 3-Bromo-2, 5-diphenylthiphenyl (cas No. 662143-74-0);
Figure BDA0003428640890000042
according to the above preparation method, preferably, the molar ratio of the compound E, 4-aminophenylboronic acid pinacol ester to tetrakis (triphenylphosphine) palladium is 1:1:0.05; the molar ratio of potassium carbonate to compound C in the mixture was 7:1.
According to the above preparation method, preferably, the solvent G is tetrahydrofuran, and the organic solvent H is dichloromethane.
According to the above-mentioned preparation method, preferably, the compound A (substance name: 2-p-aminophenyl-5-phenylthiophen, CAS number: no. 82367-01-9) having the structural formula c is commercially available as it is, or can be prepared by itself, and the preparation method thereof is substantially the same as the preparation method of the compound A having the structural formula b or E, except that the compound E is different; in the preparation of the compound A with the structural formula shown in the formula c, the structural formula of the compound E is shown in the formula c-1:
Figure BDA0003428640890000043
according to the above preparation method, preferably, the preparation method of the compound a represented by the structural formula i is: adding a compound F and palladium carbon powder (the specification of the palladium carbon powder is 10 wt%) into a solvent I, and then adding a hydrazine hydrate solution to obtain a mixture; heating the mixture to 85-90 ℃, and carrying out heating reflux reaction for 1-4h; cooling the reaction liquid to room temperature after the reaction is finished, filtering, collecting filtrate, evaporating the filtrate to dryness to obtain a solid, and separating and purifying the solid to obtain a compound A with a structural formula shown as formula i;
wherein the structural formula of the compound F is shown as formula i-1:
Figure BDA0003428640890000051
according to the above-described production method, preferably, the mass ratio of palladium-carbon powder (specification of palladium-carbon powder is 10 wt%) to compound F is 3:10; the mass ratio of the hydrazine hydrate to the compound F in the mixture is 1.16:1.
According to the preparation method, preferably, the mass fraction of hydrazine hydrate in the hydrazine hydrate solution is 80%.
According to the above preparation method, preferably, the solvent I is absolute ethanol.
In a third aspect, the invention provides an application of the benzotriazine single radical compound in preparing a magnetic material or an electronic device. The benzotriazine single-radical compound prepared by the invention has magnetism, so that the benzotriazine single-radical compound can be used for preparing magnetic materials or combining semiconductor materials for producing electronic devices.
Compared with the prior art, the invention has the positive beneficial effects that:
(1) According to the invention, several single free radicals are successfully prepared, wherein the X T measured value of the benzotriazine single free radical compound with R groups selected from the formula B or G is the maximum value of Shan Ziyou groups reported at present, namely 0.96emu K/mol and 0.93emu K/mol, so that the level of a metal-free radical complex is achieved, the introduction of AIEgens is proved to obviously enhance intermolecular spin-spin interaction, and meanwhile, the introduction of a multi-benzene ring structure is also proved to have strong influence on the performance and magnetism of the benzotriazine free radicals, so that an idea is provided for the preparation of the single free radicals.
(2) The preparation method of the benzotriazine single free radical compound provided by the invention is simple, the time cost is reduced, the raw materials are cheap and easily available, and the production cost is reduced.
Drawings
FIG. 1 shows a compound A of formula a 1 H NMR spectrum;
FIG. 2A is a compound of formula a 13 C NMR spectrum;
FIG. 3 is a mass spectrum of a compound A with a structural formula shown in a formula a;
FIG. 4 is a structural formula bOf the compound A of (2) 1 H NMR spectrum;
FIG. 5A is a compound of formula b 13 C NMR spectrum;
FIG. 6 is a mass spectrum of compound A of formula b;
FIG. 7A is a compound of formula d 1 H NMR spectrum;
FIG. 8A is a compound of formula d 13 C NMR spectrum;
FIG. 9 is a mass spectrum of compound A of formula d;
FIG. 10A shows a compound C of formula d-1 1 HNMR profile;
FIG. 11A shows a compound C of formula d-1 13 CNMR profile;
FIG. 12 is a mass spectrum of compound C shown in formula d-1;
FIG. 13A is a compound of formula e 1 HNMR profile;
FIG. 14A is a compound of formula e 13 C NMR spectrum;
FIG. 15 is a mass spectrum of compound A of formula e;
FIG. 16A is a compound C of formula f-1 1 HNMR profile;
FIG. 17A is a compound C of formula f-1 13 C NMR spectrum;
FIG. 18 is a mass spectrum of compound C of formula f-1;
FIG. 19A is a compound of formula i 1 HNMR profile;
FIG. 20A is a compound of formula i 13 C NMR spectrum;
FIG. 21 is a mass spectrum of compound A of formula i;
FIG. 22 is a mass spectrum of the benzotriazine monoradical compound prepared in example 7;
FIG. 23 is a mass spectrum of the benzotriazine monoradical compound prepared in example 8;
FIG. 24 is a mass spectrum of the benzotriazine monoradical compound prepared in example 9;
FIG. 25 is a mass spectrum of the benzotriazine monoradical compound prepared in example 10;
FIG. 26 is a mass spectrum of the benzotriazine monoradical compound prepared in example 11;
FIG. 27 is a mass spectrum of the benzotriazine monoradical compound prepared in example 12;
FIG. 28 is a mass spectrum of the benzotriazine monoradical compound prepared in example 13;
FIG. 29 is a mass spectrum of the benzotriazine monoradical compound prepared in example 14;
FIG. 30 is a mass spectrum of the benzotriazine monoradical compound prepared in example 15;
FIG. 31 is a graph showing the results of the benzotriazine single radical compound SQUID prepared in example 15 according to the present invention.
Detailed Description
The following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The experimental methods in the following examples, in which specific conditions are not specified, are all conventional in the art or according to the conditions suggested by the manufacturer; the reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail with reference to specific embodiments.
Example 1: preparation of Compound A of formula a
The preparation method of the compound A shown in the structural formula a comprises the following specific steps:
(1) Compound C (2 g,7.87 mmol), 2.41g (11.81 mmol) of pinacol phenylborate and 454.72mg (0.39 mmol) of tetrakis (triphenylphosphine) palladium (Pd [ P (C) 6 H 5 ) 3 ] 4 ) 50ml of anhydrous tetrahydrofuran was addedAdding a potassium carbonate solution (the concentration of the potassium carbonate solution is 2 mol/L) into the pyran to obtain a mixture; the mixture was heated to 90 ℃ under a blanket gas atmosphere and heated to reflux for 24h.
Wherein, the molar ratio of the compound C, the pinacol phenylborate and the tetrakis (triphenylphosphine) palladium is 1:1.5:0.05; the molar ratio of potassium carbonate to compound C in the mixture was 7:1. The structural formula of the compound C is shown as a formula a-1, and the structural formula of the compound A is shown as a formula a:
Figure BDA0003428640890000071
the specific reaction equation is shown below:
Figure BDA0003428640890000072
(2) After the reaction is finished, extracting the reaction liquid by using 40ml of dichloromethane, collecting an organic solvent layer, adding anhydrous sodium sulfate into the collected organic solvent layer for drying, filtering after drying, collecting filtrate, and evaporating the filtrate to obtain a solid a;
(3) Dissolving the solid a by using dichloromethane, purifying by chromatography through a silica gel column after dissolving, and adopting ethyl acetate: n-hexane=1: 40 to 1: and 5, collecting eluent, and evaporating the eluent under reduced pressure to remove the solvent to obtain the compound A shown in the structural formula a. The yield of compound a was 62.3%.
The prepared compound A was subjected to nuclear magnetic analysis, and the nuclear magnetic results thereof are shown in FIG. 1 and FIG. 2. Simultaneously, mass spectrometry (mass spectrometry result is shown in FIG. 3) is carried out on the prepared compound A, and HRMS (ESI) + ):[M+H] + C of (2) 16 H 14 NS calculates 252.0847 and finds 252.0838. The above results confirm that the obtained product is the target product.
Example 2: preparation of Compound A of formula b
The preparation method of the compound A with the structural formula shown in the formula b comprises the following specific steps:
(1) Compound E (2 g,8.37 mmol), 4-aminophenylboronic acid pinacol ester and tetrakis (triphenylphosphine) palladium (Pd [ P (C) 6 H 5 ) 3 ] 4 ) Adding the mixture into 60ml of anhydrous tetrahydrofuran, and then adding a potassium carbonate solution (the concentration of the potassium carbonate solution is 2 mol/L) to obtain a mixture; the mixture was heated to 85 ℃ under nitrogen and heated to reflux for 24h.
Wherein, the mol ratio of the compound E, 4-aminophenylboronic acid pinacol ester and tetrakis (triphenylphosphine) palladium is 1:1:0.05; the molar ratio of potassium carbonate to compound E in the mixture was 7:1. The structural formula of the compound C is shown as a formula b-1, and the structural formula of the compound A is shown as a formula b:
Figure BDA0003428640890000081
the specific reaction equation is shown below:
Figure BDA0003428640890000082
(2) After the reaction, 40ml of dichloromethane is adopted to extract the reaction liquid, an organic solvent layer is collected, anhydrous sodium sulfate is added into the collected organic solvent layer to be dried, the filtration is carried out after the drying, the filtrate is collected, the filtrate is evaporated to dryness to obtain a solid b,
(3) Dissolving the solid b by using dichloromethane, purifying by chromatography through a silica gel column after dissolving, and adopting ethyl acetate: n-hexane=1: 30 to 1: and 5, collecting eluent, and evaporating the eluent under reduced pressure to remove the solvent to obtain the compound A shown in the structural formula b. The yield of compound a was 45.9%.
The prepared compound A was subjected to nuclear magnetic analysis, and the nuclear magnetic results thereof are shown in FIGS. 4 and 5. Simultaneously, mass spectrometry (the mass spectrometry result is shown in FIG. 6) was carried out on the prepared compound A, and HRMS (ESI) + ):[M+H] + C of (2) 16 H 14 NS calculates 252.0847 and finds 252.0841. The above results confirm that the obtained product is the target product.
Example 3: preparation of Compound A of formula d
The preparation method of the compound A shown in the structural formula d comprises the following specific steps:
(1) Compound C (2 g,6.11 mmol), pinacol phenylborate and tetrakis (triphenylphosphine) palladium (Pd [ P (C) 6 H 5 ) 3 ] 4 ) Adding the mixture into 50ml of anhydrous tetrahydrofuran, and then adding a potassium carbonate solution (the concentration of the potassium carbonate solution is 2 mol/L) to obtain a mixture; the mixture was heated to 90 ℃ under a blanket atmosphere and was allowed to react under reflux for 24h.
Wherein, the mol ratio of the compound C, the pinacol phenylborate and the tetra (triphenylphosphine) palladium is 1:3:0.05; the molar ratio of potassium carbonate to compound C in the mixture was 7:1. The structural formula of the compound C is shown as a formula d-1, and the structural formula of the compound A is shown as a formula d:
Figure BDA0003428640890000083
(2) After the reaction is finished, extracting the reaction liquid by using 40ml of dichloromethane, collecting an organic solvent layer, adding anhydrous sodium sulfate into the collected organic solvent layer for drying, filtering after drying, collecting filtrate, and evaporating the filtrate to obtain a solid d;
(3) Dissolving the solid d by using dichloromethane, purifying by chromatography through a silica gel column after dissolving, and adopting ethyl acetate: n-hexane=1: 40 to 1: and 5, collecting eluent by volume ratio, and evaporating the eluent under reduced pressure to remove the solvent to obtain the compound A shown in the structural formula d. The yield of compound a was 54.8%.
The prepared compound a was subjected to nuclear magnetic analysis, and the nuclear magnetic results thereof are shown in fig. 7 and 8. Simultaneously, mass spectrometry (the mass spectrometry result is shown in FIG. 9) was carried out on the prepared compound A, and HRMS (ESI) + ):[M+H] + C of (2) 22 H 18 NS calculates 328.1160 and finds 328.1149. The above results confirm that the obtained product isAnd (5) marking the product.
The preparation method of the compound C shown in the structural formula d-1 comprises the following steps:
(a) Compound D (5 g,15.58 mmol), pinacol 4-aminophenylborate and tetrakis (triphenylphosphine) palladium (Pd [ P (C) 6 H 5 ) 3 ] 4 ) Adding the mixture into 60ml of anhydrous tetrahydrofuran, and then adding a potassium carbonate solution (the concentration of the potassium carbonate solution is 2 mol/L) to obtain a mixture; the mixture was heated to 85 ℃ under nitrogen and heated to reflux for 24h.
Wherein the molar ratio of the compound D, 4-aminophenylboronic acid pinacol ester and tetrakis (triphenylphosphine) palladium is 1:1:0.05, and the molar ratio of potassium carbonate to the compound D in the mixture is 7:1. The structural formula of the compound D is shown as a formula D-2;
Figure BDA0003428640890000091
(b) After the reaction is finished, extracting the reaction liquid by using 40ml of dichloromethane, collecting an organic solvent layer, adding anhydrous sodium sulfate into the collected organic solvent layer for drying, filtering after drying, collecting filtrate, and evaporating the filtrate to obtain a solid; dissolving the solid by using dichloromethane, purifying by chromatography through a silica gel column after dissolving, and adopting ethyl acetate: n-hexane=1: 30 to 1: and 5, collecting eluent, and evaporating the eluent under reduced pressure to remove the solvent to obtain the compound C shown in the structural formula d-1. The yield of compound C was 56.3%.
And carrying out nuclear magnetic analysis on the prepared compound C with the structural formula shown in the formula d-1, wherein the nuclear magnetic analysis result is shown in fig. 10 and 11. Simultaneously, mass spectrometry (the mass spectrometry result is shown in FIG. 12) was carried out on the prepared compound C, and HRMS (ESI) + ):[M+H] + C of (2) 28 H 22 NS calculates 331.8744 and finds 331.8742. The above results confirm that the obtained product is the target product.
Example 4: preparation of Compound A of formula e
The preparation method of the compound A with the structural formula shown in the formula e comprises the following specific steps:
(1) Compound E (2 g,6.34 mmol), 4-aminophenylboronic acid pinacol ester and tetrakis (triphenylphosphine) palladium (Pd [ P (C) 6 H 5 ) 3 ] 4 ) Adding the mixture into 60ml of anhydrous tetrahydrofuran, and then adding a potassium carbonate solution (the concentration of the potassium carbonate solution is 2 mol/L) to obtain a mixture; the mixture was heated to 85 ℃ under nitrogen and heated to reflux for 24h.
Wherein the molar ratio of the compound E, 4-aminophenylboronic acid pinacol ester and tetrakis (triphenylphosphine) palladium is 1:1:0.05, and the molar ratio of potassium carbonate to the compound E in the mixture is 7:1. The structural formula of the compound C is shown as a formula e-1, and the structural formula of the compound A is shown as a formula e:
Figure BDA0003428640890000101
(2) After the reaction is finished, extracting the reaction liquid by using 40ml of dichloromethane, collecting an organic solvent layer, adding anhydrous sodium sulfate into the collected organic solvent layer for drying, filtering after drying, collecting filtrate, and evaporating the filtrate to obtain a solid e;
(3) Dissolving the solid e by using dichloromethane, purifying by chromatography through a silica gel column after dissolving, and adopting ethyl acetate: n-hexane=1: 30 to 1: and 5, collecting eluent by volume ratio, and evaporating the eluent under reduced pressure to remove the solvent to obtain the compound A shown in the structural formula e. The yield of compound a was 57.0%.
The prepared compound a was subjected to nuclear magnetic analysis, and the nuclear magnetic results thereof are shown in fig. 13 and 14. Simultaneously, mass spectrometry (the mass spectrometry result is shown in FIG. 15) was carried out on the prepared compound A, and HRMS (ESI) + ):[M+H] + C of (2) 22 H 18 NS calculates 328.1160 and finds 328.1154. The above results confirm that the obtained product is the target product.
Example 5: preparation of Compound A of formula f
The preparation method of the compound A with the structural formula shown in the formula f comprises the following specific steps:
(1) Compound C (2 g,4.86 mmol), pinacol phenylborate and tetrakis (triphenylphosphine) palladium (Pd [ P (C) 6 H 5 ) 3 ] 4 ) Adding the mixture into 50ml of anhydrous tetrahydrofuran, and then adding a potassium carbonate solution (the concentration of the potassium carbonate solution is 2 mol/L) to obtain a mixture; the mixture was heated to 90 ℃ under a blanket gas atmosphere and heated to reflux for 24h.
Wherein the molar ratio of the compound C, the pinacol phenylborate and the tetra (triphenylphosphine) palladium compound C is 1:4.5:0.05, and the molar ratio of the potassium carbonate to the compound C in the mixture is 7:1. The structural formula of the compound C is shown as a formula f-1, and the structural formula of the compound A is shown as a formula f:
Figure BDA0003428640890000102
(2) After the reaction is finished, extracting the reaction liquid by using 40ml of dichloromethane, collecting an organic solvent layer, adding anhydrous sodium sulfate into the collected organic solvent layer for drying, filtering after drying, collecting filtrate, and evaporating the filtrate to obtain a solid f;
(3) Dissolving the solid f by using dichloromethane, purifying by chromatography through a silica gel column after dissolving, and adopting ethyl acetate: n-hexane=1: 40 to 1: and 5, collecting eluent by volume ratio, and evaporating the eluent under reduced pressure to remove the solvent to obtain the compound A shown in the structural formula f.
The preparation method of the compound C shown in the structural formula f-1 comprises the following steps:
(a) Compound D (5 g,12.51 mmol), 4-aminophenylboronic acid pinacol ester and tetrakis (triphenylphosphine) palladium (Pd [ P (C) 6 H 5 ) 3 ] 4 ) Adding the mixture into 60ml of anhydrous tetrahydrofuran, and then adding a potassium carbonate solution (the concentration of the potassium carbonate solution is 2 mol/L) to obtain a mixture; the mixture was heated to 85 ℃ under nitrogen and heated to reflux for 24h.
Wherein the molar ratio of compound D (5 g,12.51 mmol), 4-aminophenylboronic acid pinacol ester and tetrakis (triphenylphosphine) palladium is 1:1:0.05, and the molar ratio of potassium carbonate to compound D in the mixture is 7:1. The structural formula of the compound D is shown as a formula f-2;
Figure BDA0003428640890000111
(b) Extracting the reaction liquid by using 40ml of dichloromethane after the reaction is finished, collecting an organic solvent layer, adding anhydrous sodium sulfate into the collected organic solvent layer for drying, filtering after drying, collecting filtrate, and evaporating the filtrate to obtain a solid; dissolving the solid by using dichloromethane, purifying by chromatography through a silica gel column after dissolving, and adopting ethyl acetate: n-hexane=1: 30 to 1: and 5, collecting eluent, and evaporating the eluent under reduced pressure to remove the solvent to obtain the compound C shown in the structural formula f-1. The yield of compound C was 67.8%.
And carrying out nuclear magnetic analysis on the prepared compound C with the structural formula shown in the formula f-1, wherein the nuclear magnetic analysis result is shown in fig. 16 and 17. Simultaneously, mass spectrometry (the mass spectrometry result is shown in figure 18) is carried out on the prepared compound C, and HRMS (ESI+)] + C of (2) 10 H 7 Br 3 NS calculates 409.7849 and finds 409.7841. The above results confirm that the obtained product is the target product.
Example 6: preparation of Compound A of formula i
The preparation method of the compound A with the structural formula shown in the formula i comprises the following specific steps:
(1) Compound F (2.0 g,4.06 mmol) and palladium carbon powder (specification of palladium carbon powder is 10 wt%) were added to 100ml of absolute ethanol, and then a hydrazine hydrate solution (mass fraction of hydrazine hydrate in the hydrazine hydrate solution is 80%) was added to obtain a mixture; heating the mixture to 85 ℃, and carrying out heating reflux reaction for 2h;
wherein the mass ratio of the palladium-carbon powder (the specification of the palladium-carbon powder is 10wt%) to the compound F is 3:10, and the mass ratio of the hydrazine hydrate to the compound F in the mixture is 1.16:1; the structural formula of the compound F is shown as a formula i-1, and the structural formula of the compound A is shown as a formula i:
Figure BDA0003428640890000121
(2) After the reaction is finished, cooling the reaction solution to room temperature, filtering, collecting filtrate, evaporating the filtrate to dryness to obtain a solid i, dissolving the solid i by using dichloromethane, purifying by chromatography through a silica gel column after dissolving, collecting eluent by using a volume ratio of ethyl acetate to n-hexane=1:5 to 1:4, and removing the solvent by evaporating under reduced pressure to obtain the compound A shown in the structural formula i. The yield of compound a was 67.0%.
The prepared compound a was subjected to nuclear magnetic analysis, and the nuclear magnetic results thereof are shown in fig. 19 and 20. Simultaneously, mass spectrometry (the mass spectrometry result is shown in FIG. 21) was carried out on the prepared compound A, and HRMS (ESI) + ):[M+H] + C of (2) 34 H 27 N 2 Calculated 463.2174, found 463.2159. The above results confirm that the obtained product is the target product.
Example 7:
a benzotriazine single free radical compound has the structural formula shown as follows:
Figure BDA0003428640890000122
the preparation method of the benzotriazine single free radical compound comprises the following specific steps:
s1: compound a (1 g,3.98 mmol) and compound B were added to 30ml of anhydrous tetrahydrofuran, dissolved to obtain a mixed solution, triethylamine was added to the mixed solution, reflux-reacted at 90 ℃ for 24 hours, the reaction solution was cooled to room temperature after the reaction was completed, filtered, the filtrate was collected, and tetrahydrofuran in the filtrate was removed by evaporation under reduced pressure to obtain an intermediate product.
Wherein the molar ratio of the compound A to the compound B is 1:1.25, the molar ratio of the triethylamine to the compound A is 3:1, and the compound A is the compound A prepared in the example 1.
The structural formula of the compound B is shown as follows;
Figure BDA0003428640890000123
the specific chemical reaction equation is as follows:
Figure BDA0003428640890000131
s2: dissolving the intermediate product obtained in the step S1 in anhydrous dichloromethane, adding 1, 8-diazabicyclo [5.4.0] undec-7-ene and palladium carbon powder (the specification of the palladium carbon powder is 10 wt%), stirring in air for reaction, filtering and collecting filtrate after the reaction is finished, and removing solvent in the filtrate to obtain a solid; dissolving the solid i by using dichloromethane, purifying by chromatography through a silica gel column after dissolving, and adopting ethyl acetate: n-hexane=1: 30 to 1:20, collecting eluent, and evaporating the eluent under reduced pressure to remove the solvent to obtain the benzotriazine single radical compound (yield: 32.5%). Wherein the molar ratio of the 1, 8-diazabicyclo [5.4.0] undec-7-ene to the compound A is 2:1; the mass ratio of palladium carbon powder (specification of palladium carbon powder is 10 wt%) to compound a was 1:50.
The benzotriazine monoradical compound prepared in this example was subjected to mass spectrometry (the mass spectrometry result is shown in FIG. 22), and HRMS (ESI) + ):[M] + C of (2) 29 H 20 N 3 S is calculated as 442.1378, sought 442.1376. The above results confirm that the obtained product is the target product.
Example 8:
a benzotriazine single free radical compound has the structural formula shown as follows:
Figure BDA0003428640890000132
the preparation method of the benzotriazine single radical compound in this embodiment is basically the same as that in embodiment 7, and the difference is that: in step S1, the compound a is the compound a prepared in example 2 (the amount of the substance of the compound a is unchanged). The yield of the benzotriazine single radical compound prepared in the embodiment is 40.1%.
The benzotriazine monoradical compound prepared in the example was subjected to mass spectrometry (the mass spectrometry result is shown in FIG. 23), and HRMS (ESI) + ):[M] + C of (2) 29 H 20 N 3 S is calculated as 442.1378, sought 442.1377. The above results confirm that the obtained product is the target product.
Example 9:
a benzotriazine single free radical compound has the structural formula shown as follows:
Figure BDA0003428640890000141
the preparation method of the benzotriazine single radical compound in this embodiment is basically the same as that in embodiment 7, and the difference is that: in step S1, the compound a is a compound a having a structural formula shown in formula c (the amount of the substance of the compound a is unchanged). Compound A (substance name: 2-p-aminophenyl-5-phenylthiophen, CAS number No. 82367-01-9) having the structural formula shown in formula c is commercially available. The yield of the benzotriazine monoradical compound prepared in the embodiment is 50.9 percent
The benzotriazine monoradical compound prepared in the example was subjected to mass spectrometry (the mass spectrometry result is shown in FIG. 24), and HRMS (ESI) + ):[M] + C of (2) 29 H 20 N 3 S is calculated as 442.1378, sought 442.1375. The above results confirm that the obtained product is the target product.
Example 10:
a benzotriazine single free radical compound has the structural formula shown as follows:
Figure BDA0003428640890000142
the preparation method of the benzotriazine single radical compound in this embodiment is basically the same as that in embodiment 7, and the difference is that: in step S1, the compound a is the compound a prepared in example 3 (the amount of the substance of the compound a is unchanged). The yield of the benzotriazine single radical compound prepared in the embodiment is 47.8%.
The benzotriazine monoradical compound prepared in this example was subjected to mass spectrometry (the mass spectrometry result is shown in FIG. 25), and HRMS (ESI) + ):[M] + C of (2) 35 H 24 N 3 S is calculated as 518.1691, sought 518.1680. The above results confirm that the obtained product is the target product.
Example 11:
a benzotriazine single free radical compound has the structural formula shown as follows:
Figure BDA0003428640890000151
the preparation method of the benzotriazine single radical compound in this embodiment is basically the same as that in embodiment 7, and the difference is that: in step S1, the compound a is the compound a prepared in example 4 (the amount of the substance of the compound a is unchanged). The yield of the benzotriazine single radical compound prepared in the embodiment is 43.2%.
The benzotriazine monoradical compound prepared in this example was subjected to mass spectrometry (the mass spectrometry result is shown in FIG. 26), and HRMS (ESI) + ):[M+H] + C of (2) 35 H 25 N 3 S is calculated as 519.1769, sought 519.1747. The above results confirm that the obtained product is the target product.
Example 12:
a benzotriazine single free radical compound has the structural formula shown as follows:
Figure BDA0003428640890000152
the preparation method of the benzotriazine single radical compound in this embodiment is basically the same as that in embodiment 7, and the difference is that: in the step S1, the compound A is the compound A prepared in the example 5 (the amount of the substance of the compound A is unchanged) or the compound A (the substance name is 4- (3, 4, 5-Triphenyl-2-phenyl) benzonamine with the structure formula shown in the formula f which is purchased in the prior market, and the CAS number is 96276-75-4). The yield of the benzotriazine single radical compound prepared in the embodiment is 55.1 percent
The benzotriazine monoradical compound prepared in this example was subjected to mass spectrometry (the mass spectrometry result is shown in FIG. 27), and HRMS (ESI) + ):[M+H] + C of (2) 41 H 29 N 3 S is calculated as 595.2082, sought 595.2076. The above results confirm that the obtained product is the target product.
Example 13:
a benzotriazine single free radical compound has the structural formula shown as follows:
Figure BDA0003428640890000161
the preparation method of the benzotriazine single radical compound in this embodiment is basically the same as that in embodiment 7, and the difference is that: in step S1, the compound A is 4-aminotrianiline (the amount of the substance of the compound A is unchanged). The structural formula of the compound A is shown as a formula g (CAS number: 2350-01-8):
Figure BDA0003428640890000162
the yield of the benzotriazine monoradical compound prepared in the embodiment is 63.2 percent
The benzotriazine monoradical compound prepared in this example was subjected to mass spectrometry (the mass spectrometry result is shown in FIG. 28), and mass spectrometry [ M ]] + C of (2) 31 H 23 N 4 Calculated 451.1923, found 451.1919. The above results confirm that the obtained product is the target product.
Example 14:
a benzotriazine single free radical compound has the structural formula shown as follows:
Figure BDA0003428640890000163
the preparation method of the benzotriazine single radical compound in this embodiment is basically the same as that in embodiment 7, and the difference is that: in the step S1, the compound A is 4-trimethylaniline (the amount of substances of the compound A is unchanged), and the structural formula of the compound A is shown as a formula h (Cas number is 22948-06-7):
Figure BDA0003428640890000164
the yield of the benzotriazine single radical compound prepared in the embodiment is 55.2%.
The benzotriazine monoradical compound prepared in this example was subjected to mass spectrometry (the mass spectrometry result is shown in FIG. 29), and HRMS (ESI) + ):[M+H] + C of (2) 38 H 29 N 3 Calculated 527.2361, found 527.2356. The above results confirm that the obtained product is the target product.
Example 15:
a benzotriazine single free radical compound has the structural formula shown as follows:
Figure BDA0003428640890000171
the preparation method of the benzotriazine single radical compound in this embodiment is basically the same as that in embodiment 7, and the difference is that: in step S1, compound a was the compound a prepared in example 6 (the amount of the substance of compound a was unchanged). The yield of the benzotriazine single radical compound prepared in the embodiment is 43.3%.
The benzotriazine monoradical compound prepared in this example was subjected to mass spectrometry (the mass spectrometry result is shown in FIG. 30), and HRMS (ESI) + ):[M] + C of (2) 47 H 33 N 4 Calculated as 653.2705, found 653.2737. The above results confirm that the obtained product is the target product.
Magnetic properties of the benzotriazine monoradical compounds prepared in examples 7 to 15 of the present invention were tested:
the specific experimental operation of the magnetic performance test is as follows: the free radical samples were first dried under vacuum at 50 ℃ for 48 hours, measured using a superconducting quantum interference device (SQUID, MPMS 3). About 10mg of solid sample was added to the polycarbonate capsule and mounted in a copper tube to measure magnetic susceptibility. Measured at varying temperatures (5K. Fwdarw.300K), in 1T mode, each had a temperature stability of 20 seconds (3K in increments ranging from 5 to 50K, 4K in increments ranging from 50 to 90K, and 15K in increments ranging from 90 to 300K). The data were corrected for sample pascal constants and the diamagnetism of the polycarbonate capsules. The test results are shown in FIG. 31 (examples 7 to 15 correspond to examples A to I in this order in FIG. 31).
As can be seen from fig. 31, the benzotriazine monoradical compound prepared in example 7 exhibits antiferromagnetic interaction and is a high spin Shan Ziyou group; the benzotriazine monoradical compound prepared in example 8 exhibits antiferromagnetic interactions and is a high spin Shan Ziyou radical; the benzotriazine monoradical compound prepared in example 9 exhibits paramagnetic interactions; the benzotriazine monoradical compound prepared in example 10 exhibits antiferromagnetic interactions and is a high spin Shan Ziyou radical; the benzotriazine monoradical compound prepared in example 11 exhibits antiferromagnetic interactions and is a high spin Shan Ziyou radical; the benzotriazine monoradical compound prepared in example 12 exhibits antiferromagnetic interactions and is a high spin Shan Ziyou radical; the benzotriazine monoradical compound prepared in example 13 shows ferromagnetic interaction with temperature rise, and shows antiferromagnetic interaction, and is a high spin Shan Ziyou group; the benzotriazine monoradical compound prepared in example 14 exhibits a near paramagnetic interaction, the benzotriazine monoradical compound prepared in example 15 exhibits an antiferromagnetic interaction, and is a high spin Shan Ziyou group.
The above-described embodiments are provided to illustrate the gist of the present invention, but are not intended to limit the scope of the present invention. It will be understood by those skilled in the art that various modifications and equivalent substitutions may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.

Claims (9)

1. The benzotriazine single free radical compound is characterized by having a structural formula shown in formula 1:
Figure FDA0004157077260000011
wherein R is selected from any one of formula A, formula B, formula C, formula D, formula E, formula F, formula H and formula I;
Figure FDA0004157077260000012
2. a process for the preparation of the benzotriazine monoradical compound of claim 1 comprising the steps of:
s1: adding the compound A and the compound B into the solvent A, dissolving to obtain a mixed solution, adding triethylamine into the mixed solution, heating and refluxing for reaction for 12-36 h at the temperature of 85-90 ℃, cooling the reaction solution to room temperature after the reaction is finished, filtering, collecting filtrate, and removing the solvent in the filtrate to obtain an intermediate product; wherein the structural formula of the compound A is selected from any one of a formula a, a formula b, a formula c, a formula d, a formula e, a formula f, a formula h and a formula i;
Figure FDA0004157077260000021
the structural formula of the compound B is shown as a formula 2;
Figure FDA0004157077260000022
s2: and (2) dissolving the intermediate product obtained in the step (S1) in a solvent B, adding 1, 8-diazabicyclo [5.4.0] undec-7-ene and palladium carbon powder, stirring for reaction in an aerobic environment, filtering and collecting filtrate after the reaction is finished, removing the solvent in the filtrate to obtain a solid, and separating and purifying the solid to obtain the benzotriazine single free radical compound shown in the structural formula (1).
3. The preparation method according to claim 2, wherein in step S1, the molar ratio of compound a to compound B is 1:1.25, and the molar ratio of triethylamine to compound a is 3:1; in the step S2, the molar ratio of the 1, 8-diazabicyclo [5.4.0] undec-7-ene to the compound A is 2:1, and the mass ratio of the palladium carbon powder to the compound A is 1:50.
4. The preparation method according to claim 2, wherein the preparation method of the compound a represented by the structural formula a, formula d or formula f is: adding a compound C, pinacol phenylborate and tetrakis (triphenylphosphine) palladium into a solvent C, and then adding a potassium carbonate solution to obtain a mixture; heating the mixture to 85-90 ℃ in the atmosphere of protective gas, and carrying out heating reflux reaction for 12-36 h; extracting the reaction liquid by using an organic solvent D after the reaction is finished, collecting an organic solvent layer, evaporating the organic solvent layer to dryness to obtain a solid, and separating and purifying the solid to obtain a compound A;
wherein the structural formula of the compound C is selected from any one of a formula a-1, a formula d-1 and a formula f-1;
Figure FDA0004157077260000031
5. the method according to claim 4, wherein the molar ratio of compound C, pinacol phenylborate to tetrakis (triphenylphosphine) palladium is 1: (1.5-4.5): 0.05; the molar ratio of potassium carbonate to compound C in the mixture was 7:1.
6. The process according to claim 4, wherein the compound C represented by the formula d-1 or formula f-1 is prepared by: adding a compound D, 4-aminophenylboronic acid pinacol ester and tetrakis (triphenylphosphine) palladium into a solvent E, and then adding a potassium carbonate solution to obtain a mixture; heating the mixture to 85-90 ℃ in the atmosphere of protective gas, and carrying out heating reflux reaction for 12-36 h; extracting the reaction liquid by using an organic solvent F after the reaction is finished, collecting an organic solvent layer, evaporating the organic solvent layer to dryness to obtain a solid, and separating and purifying the solid to obtain a compound C;
wherein the structural formula of the compound D is shown as a formula D-2 or a formula f-2;
Figure FDA0004157077260000032
7. the preparation method according to claim 2, wherein the preparation method of the compound a represented by the structural formula b or e is: adding a compound E, 4-aminophenylboronic acid pinacol ester and tetrakis (triphenylphosphine) palladium into a solvent G, and then adding a potassium carbonate solution to obtain a mixture; heating the mixture to 85-90 ℃ in the atmosphere of protective gas, and carrying out heating reflux reaction for 12-36 h; extracting the reaction liquid by using an organic solvent H after the reaction is finished, collecting an organic solvent layer, evaporating the organic solvent layer to dryness to obtain a solid, and separating and purifying the solid to obtain a compound A;
wherein the structural formula of the compound E is shown as a formula b-1 or a formula E-1;
Figure FDA0004157077260000033
8. the process according to claim 7, wherein the molar ratio of compound E, 4-aminophenylboronic acid pinacol ester to tetrakis (triphenylphosphine) palladium is 1:1:0.05; the molar ratio of potassium carbonate to compound C in the mixture was 7:1.
9. The preparation method according to claim 2, wherein the preparation method of the compound a represented by the structural formula i is: adding a compound F and palladium carbon powder into a solvent I, and then adding a hydrazine hydrate solution to obtain a mixture; heating the mixture to 85-90 ℃, and carrying out heating reflux reaction for 1-4h; cooling the reaction liquid to room temperature after the reaction is finished, filtering, collecting filtrate, evaporating the filtrate to dryness to obtain a solid, and separating and purifying the solid to obtain a compound A with a structural formula shown as formula i;
wherein the structural formula of the compound F is shown as formula i-1:
Figure FDA0004157077260000041
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