CN104292151B - Novel viologen compounds and their preparation - Google Patents
Novel viologen compounds and their preparation Download PDFInfo
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- CN104292151B CN104292151B CN201310298443.9A CN201310298443A CN104292151B CN 104292151 B CN104292151 B CN 104292151B CN 201310298443 A CN201310298443 A CN 201310298443A CN 104292151 B CN104292151 B CN 104292151B
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- 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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/22—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
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Abstract
The invention relates to a series of novel viologen compounds and preparation thereof. Specifically, the invention provides a compound with a structure shown in formula I, wherein the definition of each group is described in the specification. The compound of formula I prepared by the invention has wide application in the aspects of soft material construction, photoelectric materials and solar cells.
Description
Technical Field
The invention relates to the field of organic synthesis, and particularly provides a novel viologen compound and a preparation method thereof.
Background
Viologens are a generic term for 1,1 ' -disubstituted 4,4 ' -bipyridinium salts which have a strong lack of electrical properties and are well used as photoelectron receptors in organic electronic devices such as solar cells ((a) Zahavy, s.; Seiler, m.; Marx-Tibbon, s.; Joselevich, e.; Willner, i.; Durr, h.; O ' Connor, d.; Harriman, a.angelw.chem., int.ed.1995,34, 1005.; b) Nishikitani, y.; Uchida, s.; Asano, t.; minam., Oshima, s.; Ikai, k.; Kubo, t.j.phys.chem.112, 4372. c.). In addition, the viologen compounds can realize reversible oxidation-reduction reaction by means of chemistry, photochemistry, electrochemistry and the like, and have good oxidation-reduction performance. The viologen compounds are organic electrochromic materials with excellent performance, and have good application prospects in the fields of display devices, intelligent glass, intelligent windows, automobile anti-dazzle eyepieces and the like (a) Cao Cheng, Wangzuan, chemical development, 2008, 1353, (b) Sunjian, Fuyikai, Chenzhu, Chenwei, Jiangqinglong, fine chemical engineering, 2008, 438, and (c) Mortimer, R.J.Electrochim.acta,1999,44, 2971).
The viologen derivatives reported at present are mainly constructed by introducing saturated alkane substituents on a nitrogen atom of bipyridyl, and because the saturated alkane groups do not generate a conjugation effect with the bipyridyl groups, the alkane substituents have very limited influence on the electrochemical properties of the constructed viologen derivatives regardless of the length of the viologen derivatives, and are not beneficial to regulating and controlling the electronic receiving capacity and the color change range of the viologen compounds. Polyviologen polymers incorporating multiple viologen fragments in the polymer have also been reported, but in these systems the viologen fragments are linked together using non-conjugated flexible chains such as alkyl chains or polyethylene glycol chains ((a) Lieder, m.;
c.w.j.appl.electrochem.1997,27,235; (b) choi, s.; Lee, j.w.; Ko, y.h.; Kim, k.macromolenes2002, 35,3526; (c) belitsky, j.m., Nelson, a., Stoddart, j.f.org.biomol.chem.2006,4, 250. ) The viologen units are relatively independent from each other, the conformation is not determined, and the expressed characteristic is the property of independent viologen individuals.
In view of the above, there is a lack in the art of a fully conjugated polyviologen compound with unique electrochemical properties.
Disclosure of Invention
The invention aims to provide a novel viologen compound with special oxidation-reduction characteristics and electronic effects and a preparation method thereof.
In a first aspect of the invention, there is provided a compound of formula I:
wherein the content of the first and second substances,
m is selected from the group consisting of: 1.2, 3, 4, 5;
n is selected from the group consisting of: 1.2, 3;
each R is independently selected from the group consisting of: substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C1-C30 heteroaryl;
R1and R2Each independently selected from the group consisting of: substituted or unsubstituted C1-C30 alkyl (straight or branched); substituted or unsubstituted aryl of C6-C30, substituted or unsubstituted heteroaryl of C1-C30;
wherein said substitution is by a group selected from the group consisting of: halogen, hydroxyl, carboxyl, carbonyl, aryl of C6-C30, and heteroaryl of C1-C30;
x is a compensating anion, preferably selected from the group consisting of: cl－、Br－、I－、ClO4 －、CH3COO－、CH3(C6H4)SO3 －、PF6 －、AsF6 －、BF4 －、NO3 －Or a combination thereof.
In another preferred embodiment, m is selected from the group consisting of: 1.2, 3;
the n is selected from the following group: 1. 2;
said R1And R2Each independently selected from the group consisting of: substituted or unsubstituted C1-C8 alkyl; wherein said substitution is by a group selected from the group consisting of: halogen, hydroxyl, carboxyl, carbonyl, aryl of C6-C30, and heteroaryl of C1-C30;
the R is selected from the following group: substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, o,
In another preferred embodiment, R is1And R2Each independently selected from the group consisting of: substituted or unsubstituted C1-C4 alkyl; wherein said substitution is by a group selected fromAnd (3) substitution: halogen, hydroxyl, carboxyl, carbonyl, aryl of C6-C30 and heteroaryl of C1-C30.
In another preferred embodiment, R is selected from the group consisting of: substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl,
In another preferred embodiment, the compound of formula I is selected from the group consisting of:
in the above formulae, R1And R2As defined above;
R3selected from the group consisting of: substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C1-C30 heteroaryl.
In a second aspect of the invention, there is provided a process for the preparation of a compound of formula I as described in the first aspect of the invention, said process comprising the steps of:
(4a) using a compound of formula IIa and R- (Y) in an inert solventn+1Reacting to obtain a compound shown in formula Ib; and
(4b) reacting a compound of formula Ib with a terminal alkylating agent to obtain a compound of formula I.
Wherein m = 1and n is selected from 1, 2, 3;
r, X are as defined above;
y is an amino group.
In another preferred embodiment, the terminal alkylating agent is R1-M1And R2-M2(ii) a Wherein R is1、R2Is as defined above;
M1、M2each independently selected from the group consisting of: F. cl, Br and I.
In another preferred embodiment, in said step (4a), the compound of formula IIa and R- (Y)n+1The molar ratio of (A) to (B) is 1-5: 1.
In another preferred embodiment, said step (4b) is carried out in the presence of a supporting electrolyte, preferably tetrabutylammonium hexafluorophosphate (n-Bu)4NPF6)。
In another preferred embodiment, the reaction time of step (4b) is 2-72 h.
In another preferred embodiment, the reaction temperature in the step (4b) is 50-150 ℃.
In another preferred embodiment, the method further has one or more features selected from the group consisting of:
the inert solvent is selected from the following group: water, methanol, ethanol, propanol, acetonitrile, N-dimethylformamide, dimethyl sulfoxide, 1, 4-dioxane, or N, N-dimethylacetamide, or a combination thereof; and/or
The step (4a) is carried out at 0-150 ℃; and/or
After the reaction is finished, the reaction product is washed once or for a plurality of times by using a second solvent, and is filtered to obtain a purified product.
In another preferred embodiment, the second solvent is selected from the group consisting of: methanol, acetone, tetrahydrofuran, diethyl ether, or combinations thereof.
In another preferred example, the method further comprises: after dissolving the reaction product with a second solvent and forming a second solvent solution of the reaction product, the second solvent solution of the reaction product is heated to reflux.
In another preferred embodiment, the heating time is 0.5-8 h.
In a third aspect of the invention, there is provided a process for the preparation of a compound of formula I as described in the first aspect of the invention, said process comprising the steps of:
(6a) reacting a compound shown in a formula III with a compound shown in a formula IIb in an inert solvent to obtain a compound shown in a formula Ib; and
(6b) reacting a compound shown in formula Ib with a terminal alkylating reagent to obtain a compound shown in formula I;
wherein m is selected from 1, 2, n = 1;
r, X are as defined above;
y is an amino group.
In another preferred embodiment, the molar ratio of the compound of formula III to the compound of formula IIb is 1: 0.1-10, preferably 1: 0.5-3.
In another preferred embodiment, the reaction time of step (6a) is 1 to 7 days, preferably 2 to 4 days.
In another preferred embodiment, the terminal alkylating agent is R1-M1And R2-M2(ii) a Wherein R is1、R2、M1、M2Is as defined above.
In another preferred embodiment, the reaction product of step (6b) is ion exchanged.
In another preferred embodiment, the method further has one or more features selected from the group consisting of:
the inert solvent is selected from the following group: water, methanol, ethanol, propanol, acetonitrile, N-dimethylformamide, dimethyl sulfoxide, 1, 4-dioxane, or N, N-dimethylacetamide, or a combination thereof; and/or
The step (6a) is carried out at 0-150 ℃; and/or
The reaction time of the step (6a) is 12-120 h.
In another preferred embodiment, the compound of formula III is prepared by the following process:
reacting a compound of formula IIa with Y-R-Y in an inert solvent to obtain a compound of formula IIa;
in each of the above formulae, Y is an amino group; the other groups are as defined above.
In another preferred embodiment, the molar ratio of the compound of formula IIa to Y-R-Y is 1:1 to 10, preferably 1:2 to 4.
In another preferred embodiment, the compound of formula III is ion exchanged.
In another preferred embodiment, the inert solvent is ethanol.
In another preferred embodiment, the reaction is carried out at reflux temperature, preferably at 50-150 ℃.
In another preferred embodiment, the reaction time is 2 to 48 hours, preferably 6 to 24 hours.
In a fourth aspect of the invention, there is provided the use of a compound according to the first aspect of the invention, for use in a compound selected from the group consisting of: electrochromic materials, organic solar cell materials, or soft matter materials.
In a fifth aspect of the invention, there is provided the use of a compound according to the first aspect of the invention for the preparation of an article selected from the group consisting of: building energy-saving glass, automobile anti-glare rearview mirrors, dimming glass of automobiles or airplanes, and static display.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Detailed Description
The present inventors have conducted extensive and intensive studies for a long time and unexpectedly found that fully conjugated compounds having multiple viologen units in their structures have particularly excellent electrochemical properties, and that the compounds can form multiple valence states during oxidation-reduction due to the multiple viologen units contained in the structures, and thus the viologen compounds are substantially different from the aforementioned saturated alkane-substituted mono-viologen or non-conjugated linked polyviologen polymers in terms of both electronic effect and redox characteristics.
Term(s) for
As used herein, the term "C6-C30 aryl" refers to aryl groups having 6-30 carbon atoms, including monocyclic or bicyclic aryl groups, such as phenyl, naphthyl, or the like.
The term "C1-C30 heteroaryl" refers to a heteroaryl group having 1-30 carbon atoms, such as pyrrolyl, pyridyl, furyl, or the like.
The term "C1-C30 alkyl" refers to a straight or branched chain alkyl group having 1 to 30 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, or the like.
The term "substituted" means that one or more hydrogen atoms on a group are replaced with a substituent selected from the group consisting of: halogen, hydroxyl, carboxyl, carbonyl, aryl of C6-C30 and heteroaryl of C1-C30.
Full conjugated polyviologen compound
In order to effectively regulate and control the electrochemical properties of viologen, substituents which can participate in conjugation need to be introduced, a plurality of viologen segments form a fully conjugated system due to the conjugation and connection effect of aromatic rings, the positive charges in the viologen and free radicals generated during reduction of the viologen can be delocalized in the whole compound structure, and the change of the color of the viologen in an oxidation state or a reduction state can be greatly influenced. In addition, for the co-bridged polyserine compounds, because the structures contain a plurality of viologen units, multiple valences can be formed in the oxidation-reduction process, so that the viologen compounds are essentially different from the saturated alkane substituted mono-viologen or non-conjugated linked polyserine polymers from the aspects of electronic effect and redox characteristics, have the specificity of the viologen compounds and possibly bring some unique properties.
The invention provides a class of full-conjugated multi-viologen compounds, which have a structure shown as the following formula:
wherein the content of the first and second substances,
m is selected from the group consisting of: 1.2, 3, 4, 5;
n is selected from the group consisting of: 1.2, 3;
each R is independently selected from the group consisting of: substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C1-C30 heteroaryl;
R1and R2Each independently selected from the group consisting of: substituted or unsubstituted C1-C30 alkyl (straight or branched); substituted or unsubstituted aryl of C6-C30, substituted or unsubstituted heteroaryl of C1-C30;
wherein said substitution is by a group selected from the group consisting of: halogen, hydroxyl, carboxyl, carbonyl, aryl of C6-C30, and heteroaryl of C1-C30;
x is a compensating anion, preferably selected from the group consisting of: cl－、Br－、I－、ClO4 －、CH3COO－、CH3(C6H4)SO3 －、PF6 －、AsF6 －、BF4 －、NO3 －Or a combination thereof.
Preferably, said m is selected from the group consisting of: 1.2, 3;
the n is selected from the following group: 1. 2;
said R1And R2Each independently selected from the group consisting of: substituted or unsubstituted C1-C8 alkyl; wherein said substitution is by a group selected from the group consisting of: halogen, hydroxyl, carboxyl, carbonyl, aryl of C6-C30, and heteroaryl of C1-C30;
the R is selected from the following group: substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, o,
More preferably, R is selected from the group consisting of: substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl,
In another preferred embodiment, R is1And R2Each independently selected from the group consisting of: substituted or unsubstituted C1-C4 alkyl; wherein said substitution is by a group selected from the group consisting of: halogen, hydroxyl, carboxyl, carbonyl, aryl of C6-C30 and heteroaryl of C1-C30.
Preferred compounds of formula I according to the invention are selected from the group consisting of:
preparation of full conjugated polyviologen compounds
The invention also provides a preparation method of the fully conjugated polyviologen compound.
In a preferred embodiment of the present invention, the preparation method of the compound of formula I comprises the steps of:
(4a) using a compound of formula IIa and R- (Y) in an inert solventn+1Reacting to obtain a compound shown in formula Ib; and
(4b) reacting a compound of formula Ib with a terminal alkylating agent to obtain a compound of formula I.
Wherein m = 1and n is selected from 1, 2, 3;
r, X are as defined above;
y is an amino group.
In another preferred embodiment, the terminal alkylating agent is R1-M1And R2-M2(ii) a Wherein R is1、R2、M1、M2Is as defined above.
In another preferred embodiment, in said step (4a), the compound of formula IIa and R- (Y)n+1The molar ratio of (A) to (B) is 1-5: 1.
Said step (4b) is preferably carried out in the presence of a supporting electrolyte, and in a preferred embodiment of the present invention, said supporting electrolyte is tetrabutylammonium hexafluorophosphate (n-Bu)4NPF6)。
The reaction time of each step is not particularly limited, and it is optionally judged whether the reaction is completely performed using a TLC method. In a preferred embodiment, the reaction time of step (4b) is 2-72 h.
The reaction temperature in each step is not particularly limited, and may be carried out at reflux temperature. In another preferred example, the step (4a) is carried out at 0-150 ℃; the reaction in the step (4b) is carried out at 50-150 ℃.
In another preferred embodiment, the method further has one or more features selected from the group consisting of:
the inert solvent is selected from the following group: water, methanol, ethanol, propanol, acetonitrile, N-dimethylformamide, dimethyl sulfoxide, 1, 4-dioxane, or N, N-dimethylacetamide, or a combination thereof
And/or
After the reaction is complete, the reaction product is washed with one or more second solvents and filtered to provide a purified product.
In another preferred embodiment, the second solvent is selected from the group consisting of: methanol, acetone, tetrahydrofuran, diethyl ether, or combinations thereof.
In another preferred example, the method further comprises: after the reaction product is added with the second solvent, a solution of the reaction product in the second solvent is heated to reflux.
In another preferred embodiment, the heating time is 0.5-8 h.
In another preferred embodiment of the present invention, the preparation method of the compound of formula I comprises the steps of:
(6a) reacting a compound shown in a formula III with a compound shown in a formula IIb in an inert solvent to obtain a compound shown in a formula Ib; and
(6b) reacting a compound shown in formula Ib with a terminal alkylating reagent to obtain a compound shown in formula I;
wherein m is selected from 1, 2, n = 1;
r, X are as defined above;
y is an amino group.
In another preferred embodiment, the molar ratio of the compound of formula III to the compound of formula IIb is 1: 0.1-10, preferably 1: 0.5-3.
In another preferred embodiment, the inert solvent is a solvent selected from the group consisting of: water, methanol, ethanol, propanol, acetonitrile, N-dimethylformamide, dimethyl sulfoxide, 1, 4-dioxane, or N, N-dimethylacetamide, or a combination thereof.
The reaction time of each step is not particularly limited, and it is optionally judged whether the reaction is completely performed using a TLC method. In another preferred embodiment, the reaction time of step (6a) is 1 to 7 days, preferably 2 to 4 days.
The reaction temperature in each step is not particularly limited, and may be carried out at reflux temperature. In another preferred example, the step (6a) is carried out at 0-150 ℃.
In another preferred embodiment, the terminal alkylating agent is R1-M1And R2-M2(ii) a Wherein R is1、R2、M1、M2Is as defined above.
In another preferred embodiment, the reaction product of step (6b) is ion exchanged to change the kind of compensating anion. The ion exchange may be carried out by any method conventional in the art, such as dissolving the compound in a suitable organic solvent and precipitating it by adding another anion.
In the above reaction, each raw material may be obtained by a commercially available route or prepared by a conventional method.
In another preferred embodiment, the compound of formula III is prepared by the following process:
reacting a compound of formula IIa with Y-R-Y in an inert solvent to obtain a compound of formula IIa;
in each of the above formulae, Y is an amino group; the other groups are as defined above.
In another preferred embodiment, the molar ratio of the compound of formula IIa to Y-R-Y is 1:1 to 10, preferably 1:2 to 4.
In another preferred embodiment, the reaction product of formula III is ion exchanged.
In another preferred embodiment, the inert solvent is ethanol.
In another preferred embodiment, the reaction is carried out at reflux temperature, preferably at 50-150 ℃.
In another preferred embodiment, the reaction time is 2 to 48 hours, preferably 6 to 24 hours.
Electrochromic material
The electrochromic is a phenomenon that the optical properties (transmissivity, reflectivity or absorptivity) of the material in the ultraviolet-visible light or near infrared region generate stable reversible change under the action of an applied electric field, and the material is represented as reversible change of color and transparency in appearance. Materials with electrochromic properties are then referred to as electrochromic materials. The color-changing material is the core of the color-changing device, and the organic electrochromic material is more and more widely concerned due to the characteristics of designable molecular structure, color diversity, good processing performance, low manufacturing cost and the like.
Viologen is a very special organic matter, has excellent oxidation-reduction property, can generate oxidation-reduction reaction by chemical, electrochemical, photochemical and other methods, and is accompanied with obvious color change, so that the viologen can be used as an electrochromic or photochromic material. In addition, its different redox states can donate or accept electrons. In particular, the fully conjugated polyviologen compound provided by the invention has special electrochemical performance, compared with the polyviologen polymer which is reported by the prior literature and is connected by monocviologen or nonconjugate, a plurality of viologen segments form a fully conjugated system due to the conjugated connection effect of an aromatic ring, and the reduction potential is reduced due to the conjugation effect, so that the color can be changed at a lower potential. And thus are well suited for use as excellent electron acceptors in organic reactions, or as oxidizing species. Has good application prospect in the fields of chemical catalysis, supermolecule, herbicide, photovoltaic cell and the like.
The compound can also be used for preparing electrochromic composite materials or used as electrochromic materials for preparing electrochromic devices. Preferred electrochromic devices include (but are not limited to): building energy-saving glass, automobile anti-glare rearview mirrors, dimming glass of automobiles or airplanes, static display and the like.
The main advantages of the invention
(1) The preparation method obtains a series of full conjugated compounds with multiple viologen units in the structure. Because these structures contain a plurality of viologen units, multiple valence states can be formed in the oxidation-reduction process, so that the viologen compounds are essentially different from the saturated alkane substituted mono-viologen or unconjugated linked multi-viologen polymers from the aspects of electronic effect and redox characteristics, and have particularly excellent electrochemical performance.
(2) Compared with the singly viologen or non-conjugated linked polyviologen polymers reported by the prior literature, the series of aromatic ring bridged polyviologen compounds designed and synthesized by the invention have the advantages that a plurality of viologen segments form a fully conjugated system due to the conjugated linking action of the aromatic rings, and the reduction potential is reduced due to the conjugated action, so that the color can be changed at a lower potential.
(3) In the fully conjugated polyviologen compound, the positive charge of the viologen unit and the free radical generated during reduction can be delocalized in the whole compound structure, so that the stability of the material can be further improved.
(4) Because the compound structure contains a plurality of viologen units, multiple valence states can be formed in the oxidation-reduction process of the compound, the compound has multiple oxidation-reduction energy levels, and the compound is more abundant in color change when used as a color-changing material, and the energy levels are more easily matched when used as a photoelectron receptor material in a photovoltaic cell.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are by weight.
General procedure
Synthesis of Zincke salts
Synthesis of 2, 4-dinitrochlorobenzene: in a 2000mL single neck flask, p-nitrochlorobenzene (63.64g,402mmol) and fuming nitric acid (150mL) were added and stirred at room temperature to form a yellow solution. 30mL of sulfuric acid was added and the system rapidly exothermed and formed a brown gas. After half an hour of the reaction, the reaction was not exothermic and was gradually cooled to room temperature, the system was a yellow solution, TLC showed the disappearance of the starting material point, 1000mL of water was added to quench the reaction, a large amount of yellow solid was precipitated, and 2, 4-dinitrochlorobenzene (yellow solid, 80.19g, 96% yield) was obtained after filtration and drying.1H NMR(400MHz,DMSO-d6):8.91(d,1H);8.51-8.48(dd,1H),8.08(d,1H)。
Zincke salt 1: a1000 mL single-neck flask was charged with 4, 4' -bipyridine (50 g,321 mmol), 2, 4-dinitrochlorobenzene (54 g,267 mmol), and acetone (500 mL). Heating to reflux for 24 hr to produce grey solid, cooling to room temperature, filtering, washing with acetone, adding acetone, and heating to reflux for 2-3 hr. Filtration while hot gave, after drying, 60.34g of product in 70% yield.1H NMR(400MHz,D2O)δ9.37(d,1H),9.24(d,2H),8.93-8.90(dd,1H),8.81-8.80(dd,2H),8.67(d,2H),8.26(d,1H),8.02-8.01(dd,2H)。
Zincke salt 2: a250 mL single neck flask was charged with 4, 4' -bipyridine (3.63 g, 23 mmol), 2, 4-dinitrochlorobenzene (16.46 g, 81 mmol) and acetonitrile (70 mL) and stirred to form a yellow solution which was heated to reflux for 72 h. A large amount of white precipitate formed, which was filtered while hot, and the solid obtained was added to 150mL of acetone and refluxed for 1 hour. Filtration, washing of the solid with acetone, and drying gave an off-white solid (6 g, 50% yield).1H NMR(400MHz,CD3OD)δ9.67(d,2H),9.34(d,1H),9.11(d,2H),9.00-8.97(dd,2H),8.41(d,1H)。
Example 1: synthesis of Compound P12
Step 1: zincke salt 1 (5.37 g, 15 mmol), p-phenylenediamine (0.542, 5mmol) was added to 60mL ethanol, heated to reflux for 48 hours, cooled to room temperature, filtered, and the solid dissolved in methanol. And dripping the methanol solution into a large amount of acetone, separating out a precipitate, filtering, washing a solid with acetone, and drying to obtain a product. Grey solid (0.352 g, 15% yield).1HNMR(400MHz,CD3OD)δ9.52(d,4H),8.92(d,4H),8.80(d,4H),8.35(s,4H),8.14(d,4H)。MS(ESI):m/z194.1[M-2Cl]2+
Step 2: the compound obtained in step 1 (0.233 g, 0.5 mmol), methyl iodide (1 mL, 160mmol) was added to 60mL acetonitrile. Heating to reflux for 72 hours precipitated a large amount of red solid. After cooling to room temperature, the mixture was stirred overnight with open air, filtered, and the resulting solid was washed with acetone and dried to obtain the objective compound P12 (0.308 g, yield 63%).1HNMR(400MHz,CD3CN):9.05(d,4H),8.87(d,4H),9.49-8.42(dd,8H),7.47(d,4H),6.89-6.87(dd,4H),4.41(s,6H)。13CNMR(100MHz,CD3CN) 152.47,149.95,147.44,146.81,145.22,128.51,128.25,128.00,127.96,127.82and 49.45. HRMS (MALDI-DHB) calcd C28H26N4 +[M-4Cl]418.2161, Experimental value 418.2152.
Example 2: synthesis of Compound P14
Step 1: adding Zincke salt 1 (1.95 g, 5.5 mmol), 4, 4' -biphenyldiamine (0.3 g, 1.6 mmol) into 120mL ethanol, heating to reflux for 12 h, filtering, washing the obtained solid with acetone, dissolving in 100mL anhydrous methanol to obtain orange yellow solution, adding NH4PF6Ion exchange was carried out, filtration was carried out, and the solid product was washed with acetone and dried to obtain 0.192g of hexafluorophosphate in a yield of 75%.1HNMR(400MHz,DMSO-d6):9.58(d,4H),8.93(d,4H),8.84(d,4H),8.25(d,4H),8.18(d,4H),8.12(d,4H)。13CNMR(100MHz,DMSO-d6):153.42,152.05,150.29,146.45,145.53,145.23,144.35,142.28,140.87,140.63,129.92,128.83,128.63,127.52,126.91,126.19,125.76,125.49,124.51,123.31,122.21,and120.94。MS(ESI):m/z[M-2Cl]2+232.1. HRMS (MALDI-DHB) calcd C32H24N4[M-2PF6]464.20, Experimental value C32H23N4 +463.1917。
Step 2: the compound obtained in step 1 (0.825 g, 1.55 mmol), methyl iodide (3 mL, 480 mmol) was added to 80mL of acetonitrile, heated to reflux, and reacted for 48 hours. The heating was stopped, and after cooling to room temperature, the mixture was stirred open for several hours. Filtering, washing the solid with acetone, drying to obtain 1.25g of solid, dissolving the crude product in 300mL of water, adding NH4PF6(7.5 g, 46mmol, 30eq) was subjected to ion exchange and stirred at room temperature for 6 hours. Filtration, washing of the solid with water and drying gave the title compound P14 (1.5 g, 91% yield).1HNMR(400MHz,CD3CN):9.26(d,4H),8.94(d,4H),8.63(d,4H),8.50(d,4H),8.16(d,4H),7.97(d,4H),4.48(s,6H)。13CNMR(100MHz,CD3CN) 150.86,149.32,146.62,145.56,142.39,142.15,129.52,127.29,126.97,125.31and 48.65. HRMS (MALDI-DHB) calcd C34H30N4[M-4PF6]494.2472, Experimental value 494.2465
Example 3: synthesis of Compound P15
Step 1: zincke salt 1 (3.64 g, 10 mmol), p-phenylenediamine (3.26 g, 30 mmol) was added to absolute ethanol (100 mL) and heated to reflux for 12 h. Filtration, washing of the solid with acetone and drying gave compound b-1 (a red-brown solid, 2.75g, 97% yield) which was then ion exchanged to give the hexafluorophosphate salt.1HNMR(400MHz,CD3CN):9.33(d,2H),8.89-8.88(dd,2H),8.67(d,2H),8.12-8.10(dd,2H),7.57-7.50(dd,2H),6.79-6.77(dd,2H),5.97(s,2H).
13CNMR(100MHz,CD3CN):154.22,152.26,152.14,145.05,142.02,126.69,126.07,122.72,118.26,115.54。MS(ESI):m/z248.0[M-Cl]+. HRMS (ESI) calculated value C16H14N3[M-Cl]248.12, Experimental value 248.11822.
Step 2: the compound (0.455 g, 0.81 mmol) obtained in step 1and Zincke salt 2 (0.576 g, 2mmol) were added to absolute ethanol (60 mL), heated to reflux and reacted for 84 hours. Cooled to room temperature, filtered to give a grey solid, washed with acetone, and dried to give intermediate (0.31 g, 50% yield).1HNMR(400MHz,CD3OD):9.75(d,4H),9.55(d,4H),9.08(d,4H),8.92(d,4H),8.81(d,4H),8.44-8.37(m,8H),8.16(d,4H)。13CNMR(100MHz,D2O):164.68,155.63,151.36,149.92,145.86,144.98,144.52,144.17,142.46,127.52,126.91,126.31and122.79.
MS(ESI):m/z206.5[M-4Cl]3+. HRMS (MALDI-DHB) calcd C42H32N6[M-4PF6]620.27, Experimental value 620.2683.
And step 3: adding the obtained product (0.338 g, 0.28 mmol), methyl iodide (1 mL, (160mmol) into acetonitrile (80 mL), heating to reflux, reacting for 48 hours, stopping heating, cooling to room temperature, stirring for several hours, filtering, washing the solid with acetone, drying to obtain a solid crude product, dissolving the solid crude product in 25mL of water, adding 1.5g (9.2mmol, 33eq) of NH4PF6Ion exchange was performed and stirred at room temperature for 6 hours. Filtration, washing of the solid with water and drying gave the title compound P15 (0.2 g, 90% yield).1HNMR(400MHz,CD3CN):9.34(d,4H),9.29(d,4H),8.96(d,4H),8.79(d,4H),8.68(d,4H),8.52(d,4H),8.21(s,8H),4.46(s,6H)。13CNMR(100MHz,D2O) 151.88,151.36,149.38,146.44,145.84,145.68,144.40,144.35,127.52,127.26,126.98,126.89and 48.46. HRMS (MALDI-DHB) calcd C44H38N6[M-6PF6]650.3158, Experimental value 650.3153.
Example 4: synthesis of Compound P16
Step 1: to a 50mL sealed tube was added 4, 4-diaminoterphenyl (0.7 g, 2.69 mmol) and Zincke salt 1 (3.38 g,9.41 mmol), followed by addition of ethanol (20 mL) and heating to reflux. And (5) monitoring the reaction by climbing a plate, stopping the reaction after the reaction is finished, and cooling to room temperature. The solution was transferred to a 500mL single neck flask, acetone (300 mL) was added to the flask, heated to reflux for 2 hours and filtered with suction to give 1.21g of solid product, yield: 74 percent.1H NMR(400MHz,DMSO)δ9.58(d,J=6.8Hz,4H),8.94(d,J=5.7Hz,4H),8.83(d,J=6.8Hz,4H),8.19(d,J=8.8Hz,8H),8.12–8.00(m,8H)。MS(ESI):m/z270.3[M-2Cl]2+。
Step 2: to a 30mL stopcock were added the product of step 1 (400 mg, 0.65 mmol) and anhydrous acetonitrile (3 mL), followed by iodomethane (0.8 mL). Heating to 90 deg.c in oil bath, reacting for two days, stopping reaction and cooling to room temperature. Adding acetone into the system, and performing suction filtration to obtain a brownish red solid. Dissolving the red solid with a small amount of water, adding ammonium hexafluorophosphate aqueous solution while stirring, immediately generating precipitate, and filtering to obtain the solid. After the solid was dissolved in a small amount of nitromethane, a tetra-n-butylammonium chloride solution was added to precipitate immediately, and the objective compound P16 (brown solid, 415mg, yield 71%) was obtained by filtration.1H NMR(400MHz,DMSO)δ9.75(d,J=6.8Hz,4H),9.34(d,J=6.9Hz,4H),8.99(d,J=7.0Hz,4H),8.91(d,J=6.8Hz,4H),8.23(d,J=8.7Hz,4H),8.11(d,J=8.7Hz,4H),8.06(d,J=7.7Hz,4H),8.03–8.02(m,4H),4.48(s,6H)。
Example 5: synthesis of Compound P17
Step 1: zincke salt 1 (3.62 g, 10 mmol) and benzidine (7.61 g,40 mmol) were added to 350mL ethanol and heated to reflux for 12 hours, with a large amount of red solid formed. The mixture was filtered while hot, and the obtained solid was added to 500mL of acetone, refluxed for 2 hours, filtered while hot, and dried to obtain 2.82g of a red solid with a yield of 80%. After ion exchange, hexafluorophosphate can be obtained.1HNMR(400MHz,CD3CN):9.06(d,2H),8.87(d,2H),8.88(d,2H),8.48(d,2H),7.90(t,4H),7.75(d,2H),7.53(d,2H),6.77(d,2H)。13CNMR(100MHz,CD3CN):152.83,151.09,149.59,144.99,143.48,140.61,139.72,127.72,126.36,125.25,124.95,124.80,122.00,121.89and114.24。
MS(ESI):m/z[M-Cl]+324.1. HRMS (ESI) calculated value C22H18N3 +[M-Cl]324.15, Experimental value 324.1495.
Step 2: the compound (0.41 g, 1.14 mmol) obtained in step 1, Zincke salt 2 (0.28 g, 0.5 mmol) was added to 50mL of anhydrous ethanol, heated to reflux and reacted for 72 hours. Filtration gave a brown-grey solid which, after washing with acetone and drying, gave 0.341g of product in 91% yield. After ion exchange, hexafluorophosphate can be obtained.
1HNMR(400MHz,CD3CN):9.31(s,4H),9.12(d,4H),8.90(d,4H),8.73(d,4H),8.55(d,4H),8.13(t,8H),7.99-7.93(dd,12H)。13CNMR(100MHz,CD3CN):153.43,151.17,149.07,145.95,145.39,142.30,140.60,128.72,126.68,125.68,125.32and122.09。MS(ESI):m/3z257.4[M-4Cl]3+. HRMS (MALDI-DHB) calcd C54H40N6[M-4PF6]772.33, Experimental value 772.3309.
And step 3: the compound obtained in step 2 (0.51 g, 0.56 mmol), methyl iodide (3 mL, 480 mmol) was added to 80mL of acetonitrile and heated to reflux for 48 hours. StopThe mixture is cooled to room temperature and then stirred for several hours. Filtering, washing the solid with acetone, drying to obtain 0.689g of solid, dissolving the crude product in 200mL of water, adding NH4PF6(6.37 g, 39mmol, 68eq) was ion exchanged, heated at reflux for 3 hours, cooled to room temperature, filtered, washed with water and dried to give the title compound P17 (0.60 g, 90% yield).1HNMR(400MHz,CD3CN):9.30(d,4H),9.25(d,4H),8.91(d,4H),8.74(d,4H),8.63(d,4H),8.49(d,4H),8.18(t,8H),7.99(t,8H),4.45(s,6H)。13CNMR(100MHz,CD3CN) 150.89,150.56,149.33,146.61,145.69,145.58,142.43,142.40,142.24,142.19,129.58,129.56,127.49,127.31,127.01,125.36,125.33and 48.69. HRMS (MALDI-DHB) calcd C56H46N6 +[M-6PF6]802.3774, Experimental value 802.3770.
Example 6: synthesis of Compound P18
Step 1: zincke salt 1 (3.4 g, 9.48 mmol), 1, 5-diaminonaphthalene (0.5 g, 3.16 mmol) were added to 20mL ethanol, heated to reflux for 24 hours, filtered, and the resulting solid was refluxed with 100mL acetone for 2 hours, filtered to give a pale yellow solid 1.18g, 74% yield.1H NMR(400MHz,MeOD)δ9.45(d,J=5.8Hz,4H),8.94(d,J=4.8Hz,4H),8.86(d,J=5.9Hz,4H),8.23(d,J=6.4Hz,2H),8.17(d,J=4.8Hz,4H),8.02(q,J=8.8Hz,4H)。MS(ESI):m/z438.2[M-2Cl]+。
Step 2: the compound obtained in step 1 (0.4 g, 0.78 mmol), methyl iodide (0.5 mL, 7.9 mmol) was added to 15mL of acetonitrile, heated to reflux, and reacted for 48 hours. Heating was stopped, cooled to room temperature and filtered, the solid was washed with dichloromethane and dried to give the title compound P18 (solid 0.69g, 90% yield).1HNMR(400MHz,MeOD)δ9.55(d,J=5.8Hz,4H),9.10(d,J=4.8Hz,4H),8.86(d,J=5.9Hz,4H),8.23(d,J=6.4Hz,2H),8.17(d,J=4.8Hz,4H),8.02(q,J=8.8Hz,4H)，4.48(s,6H)。MS(ESI):m/z468.1[M-4I]+。
Example 7: synthesis of Compound P19
Step 1:1, 3, 5-tris (4-aminophenyl) benzene (1.06g,3.02mmol) and Zincke salt 1(4.89g,13.6mmol) were dissolved in 20mL of DMSO, reacted at 80 ℃ for three days to precipitate a large amount of solid, the heating was stopped and the solid was naturally cooled to room temperature, and poured into 100mL of THF: Et2Filtering in O/1:1, collecting solid, washing the solid with 600mL, collecting filtrate, removing solvent under reduced pressure to obtain light yellow solid, dissolving again with 300mL methanol, adding 2.00g NH4PF6A large amount of solid precipitated and was collected by filtration. Performing flash column chromatography, loading by dry method, eluting with (MeCOMe: CH)2Cl2/9:1,MeCOMe,MeCOMe:NH4PF650mg in 500mL and 150mg in 500 mL). The resulting solid was washed with 60mL of water and dried in vacuo to give 0.76g of a pale yellow solid in 21% yield.1H NMR(400MHz,CD3CN)δ(ppm):9.13(d,J=6.8Hz,6H),8.90(d,J=6.0Hz,6H),8.54(d,J=6.4Hz,6H),8.28(d,J=8.8Hz,6H),8.23(s,3H),7.96(d,J=8.4Hz,6H),7.91(d,J=6.0Hz,6H)。13CNMR(100MHz,CD3CN)δ(ppm):156.12,152.33,145.91,144.35,143.06,141.97,141.5,130.50,127.60,127.37,127.09,126.04,122.99。MS(ESI)m/z:257.4[M-3PF6 -]3+.HRMS(ESI):Calcd for C54H39N63 3+[M-3PF6 -]3+257.1073, experimental value 257.1083.
Step 2: the compound obtained in step 1 (0.10 g,0.083 mmol) and n-Bu4NPF6(0.48g,1.25mmol) is dissolved in acetonitrile (6 mL), methyl iodide (0.483 g,1.25mmol) is added, the mixture is heated and refluxed for 12 hours, then methyl iodide (0.483 g,1.25mmol) is added, the reflux reaction is continued for 24 hours, and the heating is stopped and the mixture is naturally cooled to the room temperature. The solid was collected by filtration and washed with a small amount of acetonitrile. The resulting solid was dissolved in DMSO (5 mL), heated to 80 ℃ and n-Bu added4NPF6(1.0 g), at this temperature for 30 minutes, a solid precipitated, and 30mL of THF/Et was added2O/2:1, filtering, collecting solid, respectively using 20The solid was washed with mL THF and MeCOMe. Drying in vacuo afforded the title compound P19 (pale yellow solid, 60mg, 70.2% yield).1H NMR(D2O,400MHz)δ:9.43(d,J=6.8Hz,6H),9.05(d,J=6.4Hz,6H),8.71(d,J=6.8Hz,6H),8.58(d,J=6.4Hz,6H),8.21(s,3H),8.18(d,J=8.4Hz,6H),7.97(d,J=8.8Hz,6H),4.48(s,9H)。
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.
Claims (6)
1. A process for preparing a compound of formula I:
wherein R is1And R2Each independently is CH3(ii) a The R is selected from the following group: substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted biphenyl; wherein said substitution is by a group selected from the group consisting of: halogen, hydroxy, carboxy;
x is selected from the group consisting of: cl－、Br－、I－、ClO4 －、CH3COO－、CH3(C6H4)SO3 －、PF6 －、AsF6 －、BF4 －、NO3 －Or a combination thereof;
characterized in that the method comprises the steps of:
(6a) reacting a compound shown in a formula III with a compound shown in a formula IIb in an inert solvent to obtain a compound shown in a formula Ib; and
(6b) reacting a compound shown in formula Ib with a terminal alkylating reagent to obtain a compound shown in formula I;
wherein m is selected from 2, n = 1;
y is an amino group.
2. The method of claim 1, wherein the compound of formula I is selected from the group consisting of:
3. the method of claim 1, wherein the inert solvent is a solvent selected from the group consisting of: water, methanol, ethanol, propanol, acetonitrile, N-dimethylformamide, dimethyl sulfoxide, 1, 4-dioxane, or N, N-dimethylacetamide, or a combination thereof.
4. The method of claim 1, wherein step (6a) is performed at 0 to 150 ℃.
5. The method of claim 1, wherein the reaction time of step (6a) is 12-120 h.
6. The process of claim 1, wherein the compound of formula III is prepared by:
reacting a compound of formula IIa with Y-R-Y in an inert solvent to obtain a compound of formula IIa;
in the above formulae, the groups are as defined in claim 1.
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