CN111217796A - Spiro-dipyrromethene/dipyrromethene compounds and preparation method and application thereof - Google Patents

Spiro-dipyrromethene/dipyrromethene compounds and preparation method and application thereof Download PDF

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CN111217796A
CN111217796A CN201811419437.3A CN201811419437A CN111217796A CN 111217796 A CN111217796 A CN 111217796A CN 201811419437 A CN201811419437 A CN 201811419437A CN 111217796 A CN111217796 A CN 111217796A
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alkyl
compound
dipyrromethene
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CN111217796B (en
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胡德辉
陈颖盈
胡维捷
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Shanghai Yage Biotechnology Co Ltd
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    • C07D403/14—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 three or more hetero rings
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    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
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Abstract

The invention discloses a spiro-dipyrromethane/dipyrromethene compound and a preparation method and application thereof. The spiro-dipyrromethene compound is a colorless compound, has no absorption and fluorescence in a visible light region, but can change color under certain conditions, such as alkali liquor or electrolysis, so as to generate a strong absorption dipyrromethene compound. The response process from no background signal to strong signal output is realized, and the spectral change range of the dye is far higher than that of the conventional dye, so that the application prospect of the dye is greatly improved. The preparation method is simple, and the reaction conditions are mild; the spiro-dipyrromethane/dipyrromethene compound can be used as an alkali electrochromic device or an electrochromic device.

Description

Spiro-dipyrromethene/dipyrromethene compounds and preparation method and application thereof
Technical Field
The invention relates to a specially modified spiro-dipyrromethene/dipyrromethene compound and a preparation method and application thereof, belonging to the technical field of spiro-dipyrromethene/dipyrromethene compounds and preparation thereof.
Background
The dipyrromethene compounds have stronger absorption due to intramolecular conjugation, and are easy to coordinate with electron-deficient atoms to form fluorescent molecules with high quantum efficiency, and the like. For example, BODIPY, i.e. dipyrromethene and BF3The dipyrromethene fluoroboron compound formed by coordination has the advantages of high quantum efficiency, narrow spectrum, easy modification, stable chemical environment, adjustable spectral range and the like, and is widely used as a fluorescent dye. And dipyrromethane has no absorption in a visible light region because the meso-position C atom is in a saturated state and has no conjugation effect.
The conventional compound probes affect the distribution of charges in molecules, so that the spectrum of the compound probes is changed, and the compound probes are identified and qualitatively and quantitatively analyzed through the change (wavelength, intensity and the like) of the spectrum. However, the spectral change of the process is usually small and is easily interfered by the background signal. The spectrum variation range before and after recognition can be greatly increased by changing the conjugation degree of the molecule. The conjugation degrees of dipyrromethene and dipyrromethene are significantly different, and if the mutual transformation between dipyrromethene and dipyrromethene can be realized, the spectrum change range is much higher than that of the conventional dye due to the change of the conjugation degree.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a spiro-dipyrromethene/dipyrromethene compound with a novel structure, wherein the molecule of the spiro-dipyrromethene compound has no color or fluorescence, but the spiro-dipyrromethene compound is rapidly changed into dipyrromethene in an alkaline solution or an electrolysis process, the dipyrromethene compound is a colored molecule, the process realizes a response process from no background signal to strong signal output, and the spectral change range of the compound is far higher than that of a conventional dye, so that the application prospect of the compound is greatly improved.
The invention aims to provide a spiro-dipyrromethene/dipyrromethene compound and a preparation method thereof.
Another object of the present invention is to provide the use of the spiro-dipyrromethene/dipyrromethene compounds described above as base-induced color changing devices.
It is still another object of the present invention to provide the use of the spiro-dipyrromethene/dipyrromethene compounds described above as electrochromic devices.
The purpose of the invention is realized by the following technical scheme:
a spiro-dipyrromethane having the structure shown in formula (I):
Figure BDA0001880244080000021
wherein R is1、R2、R3、R4、R5、R6Identical or different, independently of one another, from the group consisting of H, alkyl, -alkyl-COO-alkyl, -alkyl-OCO-alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heteroaryl, heteroaralkyl, amino, quaternary amine, nitro, nitrile, -SO3H、-CO-R8、-COO-R9、-CO-NR10R11A halogen; and said R is1、R2、R3、R4、R5、R6At least one of them is the following group: quaternary amine, nitro group, nitrile group, -SO3H、-CO-R8、-COO-R9、-CO-NR10R11Halogen, alkynyl; wherein R is8、R9、R10、R11The same or different, optionally H, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heteroaryl, heteroaralkyl;
R1’、R2’、R3’、R4' same or different, independently from each other, are selected from the group consisting of H, -alkyl-COO-alkyl, -alkyl-OCO-alkyl, amino, alkoxy, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, aryloxy, heteroaryl, heteroaralkyl;
R7is selected from- (NR)12) -, -O-; wherein R is12Selected from H, alkylA group, amino, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heteroaryl, heteroaralkyl;
r is as defined above1、R2、R3、R4，R5、R6、R7、R1’、R2’、R3’、R4In the groups of the definition of' said alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heteroaryl, heteroaralkyl groups may be optionally substituted by one or more substituents, which may be the same or different, independently from each other selected from alkyl, alkoxy, halogen, nitro.
In a preferred embodiment, R is5、R6is-COO-alkyl or nitrile group.
In another preferred embodiment, R is3、R4is-COO-alkyl or nitrile group.
In another preferred embodiment, R is7is-O-or- (NR)12) -, wherein R12Selected from alkyl groups.
In another preferred embodiment, in the compound represented by the formula (I), R is5、R6is-COO-alkyl, R7is-O-, R1、R2、R3、R4、R1’、R2’、R3’、R4' same or different, independently from each other, are selected from H, alkyl, -alkyl-COO-alkyl, -alkyl-OCO-alkyl, cycloalkyl; the alkyl or cycloalkyl groups may be further substituted by alkyl or halogen.
In another preferred embodiment, in the compound represented by the formula (I), R is3、R4is-CN, R7Is- (NR)12) -, wherein R12Selected from alkyl, R1、R2、R5、R6、R1’、R2’、R3’、R4' same or different, independently from each other, are selected from H, alkyl, -alkyl-COO-alkyl, -alkyl-OCO-alkyl, cycloalkyl; the alkyl or cycloalkyl groups may be further substituted by alkyl or halogen.
In a good priorityIn selected embodiments, R is1’、R2’、R3’、R4' is H.
In a preferred embodiment, the compound of formula (I) is selected from the structures of formula (Ia) and formula (Ib):
Figure BDA0001880244080000031
the invention also provides a preparation method of the compound shown in the general formula (I), which is characterized by comprising the following steps:
Figure BDA0001880244080000041
wherein R is1、R2、R3、R4、R5、R6、R7、R1’、R2’、R3’、R4' as defined above;
1) dissolving the compound of the general formula (1) and the compound of the general formula (2) in an organic solvent, mixing with the compound of the general formula (3), and reacting to obtain a compound of the general formula (4);
2) reacting the compound of the general formula (4) obtained in the step 1) with an oxidant to obtain a compound of a general formula (I);
according to the invention, in step 1), the reaction is preferably carried out at room temperature and the reaction time is preferably 8 to 20 hours, for example 12 hours. The organic solvent may be any solvent that is conventional in the art, as long as it can dissolve the reactant and does not react with the reactant. Preferred are Dichloromethane (DCM), Tetrahydrofuran (THF) and acetonitrile (CH)3CN). The obtained compound of the general formula (4) can be separated and purified or directly used for the next reaction without separation and purification.
According to the present invention, preferably, the solution after the reaction in step 1) is poured into water, extracted with dichloromethane (preferably 3 times), the organic phase is washed with saturated aqueous sodium bicarbonate solution (preferably 2 times), and spin-dried to give the compound of formula (4). Preferably, the compound of the general formula (4) obtained above is purified by silica gel column chromatography, preferably using a mixed system of petroleum ether and ethyl acetate in a volume ratio of (1-5):1, for example 2:1 or 3: 1.
According to the present invention, in step 2), the reaction is carried out in an organic solvent, which may be any solvent that is conventional in the art, as long as it can dissolve the reactant and does not react with the reactant. The organic solvent is, for example, dichloromethane, tetrahydrofuran, acetonitrile, or the like.
According to the invention, in step 2), the solution obtained after the reaction in step 1) or the purified compound of formula (4) is dissolved in an organic solvent and mixed with an oxidizing agent for reaction.
Preferably, the oxidizing agent is selected from dichlorodicyanoquinone (DDQ) or Chloranil (chlorenil). The oxidizing agent is preferably added to the reaction system at a time.
According to the invention, the compound of formula (I) obtained above is preferably purified by column chromatography on silica gel, preferably using an ethyl acetate-petroleum ether 1 (5-9) developing system.
The invention also provides a dipyrromethene compound, the structure of which is shown as the following general formula (II):
Figure BDA0001880244080000051
wherein R is1、R2、R3、R4、R5、R6、R7、R1’、R2’、R3’、R4' as defined above.
In a preferred embodiment, R is5、R6is-COO-alkyl or nitrile group.
In another preferred embodiment, R is3、R4is-COO-alkyl or nitrile group.
In another preferred embodiment, R is7is-O-or- (NR)12) -, wherein R12Selected from alkyl groups.
In another preferred embodiment, in the compound represented by the formula (II), R5、R6is-COO-alkyl, R7is-O-, R1、R2、R3、R4、R1’、R2’、R3’、R4' same or different, independently from each other, are selected from H, alkyl, -alkyl-COO-alkyl, -alkyl-OCO-alkyl, cycloalkyl; the alkyl or cycloalkyl groups may be further substituted by alkyl or halogen.
In another preferred embodiment, in the compound represented by the formula (II), R3、R4is-CN, R7Is- (NR)12) -, wherein R12Selected from alkyl, R1、R2、R5、R6、R1’、R2’、R3’、R4' same or different, independently from each other, are selected from H, alkyl, -alkyl-COO-alkyl, -alkyl-OCO-alkyl, cycloalkyl; the alkyl or cycloalkyl groups may be further substituted by alkyl or halogen.
In a preferred embodiment, said R is1’、R2’、R3’、R4' is H.
In a preferred embodiment, the compound of formula (II) is selected from the structures of formulae (IIa) and (IIb) below:
Figure BDA0001880244080000061
the invention also provides a preparation method for preparing the general formula (II), which comprises the step of dissolving the compound of the general formula (I) in an alkaline solution or electrolyzing the compound of the general formula (I).
The compounds of formula (I) described herein are colorless and fluorescent, while the compounds of formula (II) are colored. The compound of the general formula (I) can be converted into a compound of a general formula (II) in an alkaline solution, and the compound of the general formula (II) is converted into the compound of the general formula (I) in a neutral or acidic solution. In addition, the compound of the general formula (I) can be converted into the compound of the general formula (II) in the electrolytic process, and after the electrode is replaced, the compound of the general formula (II) can be converted into the compound of the general formula (I). That is, the compound can be rapidly and reversibly transformed between a spiro ring state (compound of general formula (I)) and an open ring state (compound of general formula (II)), thereby realizing a colorless-colored mutual transformation.
Figure BDA0001880244080000062
The invention also provides the application of the compound of the general formula (I) or the compound of the general formula (II) in an alkali-induced color-changing device.
The invention also provides application of the compound of the general formula (I) or the compound of the general formula (II) in an electrochromic device.
The invention has the beneficial effects that:
the invention discloses a spiro-dipyrromethane/dipyrromethene compound and a preparation method and application thereof. The spiro-dipyrromethene compound is a colorless compound, has no absorption and fluorescence in a visible light region, but can change color under certain conditions, such as alkali liquor or electrolysis, so as to generate a strong absorption dipyrromethene compound. The response process from no background signal to strong signal output is realized, and the spectral change range of the dye is far higher than that of the conventional dye, so that the application prospect of the dye is greatly improved. The preparation method is simple, and the reaction conditions are mild; the spiro-dipyrromethane/dipyrromethene compound can be used as an alkali electrochromic device or an electrochromic device.
Definition and description of terms
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 the claimed subject matter belongs. All patents, patent applications, and publications cited herein are incorporated by reference in their entirety unless otherwise indicated. If there are multiple definitions of terms herein, the definition in this section controls.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the subject matter of the application. In this application, the use of "or", "or" means "and/or" unless stated otherwise. Furthermore, the term "comprising" as well as other forms, such as "includes," "including," and "containing," are not limiting.
The alkyl group represents a linear or branched alkyl group having 1 to 10 carbon atoms, preferably a linear or branched alkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, etc.
The alkoxy represents a linear or branched alkoxy group having 1 to 10 atoms, preferably a linear or branched alkoxy group having 1 to 6 carbon atoms.
The alkenyl group represents a linear or branched alkenyl group having 2 to 10 carbon atoms, preferably a linear or branched alkenyl group having 2 to 6 carbon atoms, for example, ethylene, propylene, butene, etc.
The alkynyl group represents a linear or branched alkynyl group having 2 to 10 carbon atoms, preferably a linear or branched alkynyl group having 2 to 6 carbon atoms, for example, acetylene, propyne, butyne and the like.
The cycloalkyl group represents a carbocyclic ring having 3 to 8 carbon atoms, preferably a carbocyclic ring having 3 to 6 carbon atoms, for example, cyclopentyl, cyclohexyl or cycloheptyl, etc.
The aryl group is understood to preferably mean a mono-, bi-or tricyclic hydrocarbon ring having a monovalent or partially aromatic character with 6 to 20 carbon atoms, preferably "C6-14Aryl ". The term "C6-14Aryl "is to be understood as preferably meaning a mono-, bi-or tricyclic hydrocarbon ring having a monovalent or partially aromatic character with 6,7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms (" C6-14Aryl group "), in particular a ring having 6 carbon atoms (" C6Aryl "), such as phenyl; or biphenyl, or is a ring having 9 carbon atoms ("C9Aryl), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C10Aryl radicals), such as tetralinyl, dihydronaphthyl or naphthyl, or rings having 13 carbon atoms ("C13Aryl radicals), such as the fluorenyl radical, or a ring having 14 carbon atoms ("C)14Aryl), such as anthracenyl.
The heteroaryl group is understood to be monocyclic, bicyclic and tricyclic ring systems containing 5 to 20 ring atoms, 5 to 14 ring atoms, or 5 to 12 ring atoms, or 5 to 10 ring atoms, or 5 to 6 ring atoms, at least one of which is aromatic, and at least one of which contains one or more heteroatoms (e.g., N, O, S, Se, etc.), wherein each ring system contains a ring of 5 to 7 atoms with one or more attachment points to the rest of the molecule. The heteroaryl group is optionally substituted with one or more substituents described herein. In some embodiments, a heteroaryl group of 5-10 atoms contains 1,2,3, or 4 heteroatoms independently selected from O, S, Se and N. In other embodiments, a 5-6 atom heteroaryl group contains 1,2,3, or 4 heteroatoms independently selected from O, S, Se and N.
Examples of monocyclic rings of heteroaryl groups include, but are not limited to, thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl and the like and their benzo derivatives, such as benzofuranyl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, benzotriazolyl, indazolyl, indolyl, isoindolyl and the like; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the like, and benzo derivatives thereof, such as quinolyl, quinazolinyl, isoquinolyl, and the like; or azocinyl, indolizinyl, purinyl and the like and benzo derivatives thereof; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, and the like.
The aryloxy group means an aryloxy group, i.e., -O-aryl.
The arylalkynyl group refers to arylalkynyl, i.e. -alkynyl-aryl.
The aralkyl group refers to an arylalkyl group, i.e., -alkyl-aryl.
The heteroarylalkyl refers to a heteroarylalkyl group, i.e., -alkyl-heteroaryl.
Said amino group represents the group-NR1 2Wherein R is1Identical or different, independently of one another, from the group consisting of H, alkyl, amino, aryl, heteroaryl.
The quaternary amine is-NR2 3Wherein R is2Identical or different, independently of one another, from the group consisting of H, alkyl, aryl, heteroaryl, heterocyclyl.
Drawings
FIG. 1 is a graph showing the change in absorption spectrum under the action of acid and base of a compound represented by the formula (Ia) prepared in example 1.
Figure 2 electrochromic process of the cell prepared in example 4.
Figure 3 electrochromic process of the cell prepared in example 5.
FIG. 4 crystal structure of spiro compound of formula (Ia) prepared in example 1.
Detailed Description
The following series of specific examples are given to further illustrate the present invention, but the present invention is not limited to these specific examples, and any modification of the present invention by those skilled in the art, such as replacing DDQ with other oxidizing agents, which would achieve similar results, is also included in the present invention.
The English name of dichlorodicyanoquinone is 2,3-Dichloro-5, 6-dicaano-1, 4-benzoquinone.
Example 1
The preparation of the compound of formula (Ia) (3, 5-diethoxycarbonyl-1, 2,6, 7-tetramethyl-meso-isobenzofuran-dipyrrole) is described in the following reaction scheme:
Figure BDA0001880244080000101
600mg (3.588mmol) of pyrrolate (Compound 1a) and 244.8mg (1.632mmol) of o-carboxyphenyltolualdehyde (Compound 3a) are dissolved in 30ml of acetonitrile and stirred for dissolution and stirred at room temperature overnight. The reaction solution was concentrated and separated by column chromatography (eluent petroleum ether/ethyl acetate volume ratio 2:1) to give 240mg of the target product (4 a).
200mg (0.43mmol) of Compound 4a was dissolved in 20ml of dry dichloromethane, and 155.7mg (0.686mmol, 1.6eq.) of dichlorodicyanobenzoquinone was added to the reaction system in one portion, followed by stirring at room temperature for 2 hours.
The resulting reaction mixture was washed with 1M HCl (hydrochloric acid solution) and extracted with dichloromethane, and the organic phase was washed with saturated NaCl solution and dried over anhydrous sodium sulfate to give a crude product. The crude product was concentrated and separated by column chromatography using ethyl acetate and petroleum ether at a 1:5 eluent volume ratio to give 115mg of product in 47.6% yield.
Characterization of the Compound of formula (Ia):
1H NMR(400MHz,CDCl3)δ7.99(s,1H),7.75(d,1H),7.64(t,1H),7.26(m,2H),5.30(s,1H),4.26(d,4H),2.22(s,6H),1.68(s,6H),1.33(t,6H).
ESI-MS m/z(C26H28N2O6):465.2[M+H+],463.19[M-H](theoretical value: M464.19).
Example 2
The preparation of the compound (2, 6-dinitrile-1, 3,5, 7-tetramethyl-meso-benzoylethylamine-dipyrromethene) shown in the formula (Ib) has the following relevant reaction route:
Figure BDA0001880244080000111
200mg (1.667mmol) of nitrile pyrrole (compound 1b) and 180mg (1.017mmol) of o-formylethylamine benzaldehyde (compound 3b) were dissolved in 15ml of methylene chloride and stirred overnight at room temperature. 302.8mg (1.334mmol, 1.6eq.) of dichlorodicyanobenzoquinone were added to the reaction system in one portion and stirred at room temperature for 2 hours.
The resulting reaction mixture was washed with 1M HCl (hydrochloric acid solution) and extracted with dichloromethane, and the organic phase was washed with saturated NaCl solution and dried over anhydrous sodium sulfate to give a crude product. The crude product was concentrated and separated by column chromatography using ethyl acetate and petroleum ether in an eluent volume ratio of 1:9 to give 75mg of product in 20.2% yield.
Characterization of the compound of formula (Ib):
1H NMR(400MHz,CDCl3)δ7.68(s,2H),7.52(m,1H),7.48(m,1H),3.25(4,2H),2.12(s,6H),1.30(t,6H),1.04(t,3H).
ESI-MS m/z(C24H23N5O):398.49[M+H+](theoretical value: 398.48[ M + H ]])。
The synthesis of the compound of formula (Ib) is not limited by this reaction scheme. Compound 3b in this example is replaced by compound 3a, compound 4a 'is synthesized and then acylated with an amino compound (e.g., ethylamine) to give compound 4b, which is then reacted as described above to give compound (Ib), or compound Ia' is synthesized and then acylated with an amino compound to give compound Ib. The details are as follows:
Figure BDA0001880244080000112
example 3
Preparing an alkali-induced color-changing device: the compound represented by the formula (Ia) prepared in example 1 was prepared in a 0.1M ethanol solution. Preparing 0.1M NaOH ethanol solution from NaOH (sodium hydroxide), and adding the NaOH ethanol solution into the ethanol solution containing the compound shown in the formula (Ia), wherein the solution is rapidly changed from colorless to red. The red system returns to the colorless system upon further addition of acid.
FIG. 1 is a graph showing the change in absorption spectrum under the action of acid and base of a compound represented by the formula (Ia) prepared in example 1.
The system can generate color reaction under the action of alkali solution and can be reduced into a colorless system under the action of acid, and the process is reversible. Thus, reversible acid-base color changing devices can be prepared using the compounds.
Example 4
Preparation of electrochromic device (Ia): the compound of formula (Ia) prepared in example 1 was dissolved in 0.1M acetonitrile containing 0.1M tetrabutylammonium hexafluorophosphate (TBAPF)6) As a supporting electrolyte. The above solutions were added to a cathode and an anode, respectively, and electrolysis was carried out at 1.5V under a current of 100 mA.
As shown in FIG. 2, the solutions in the 4 reaction vessels were all acetonitrile solutions containing the compound represented by the formula (Ia). Wherein, A represents a cathode and B represents an anode in the left figure; during electrolysis, the acetonitrile solution containing the compound represented by (Ia) is reduced to red at the cathode, and the acetonitrile solution containing the compound represented by (Ia) is kept colorless at the anode.
The right side of the figure shows the electrolysis result after exchanging the anode and the cathode, wherein A represents the anode and B represents the cathode; during the electrolysis, it was found that the cathode of the acetonitrile solution containing the compound represented by (Ia) gradually changed from colorless to red, and the anode of the acetonitrile solution containing the compound represented by (Ia) gradually changed in color. It can be seen that the electrochromism of the compounds of formula (Ia) is a reversible process. The red color appears dark black in fig. 2 due to the drawing color.
Example 5
Preparation of electrochromic device (Ib): the compound represented by the formula (Ib) prepared in example 2 was dissolved in 0.1M acetonitrile containing 0.1M tetrabutylammonium hexafluorophosphate (TBAPF)6) As a supporting electrolyte. The above solutions were added to a cathode and an anode, respectively, and electrolysis was carried out at 1.5V under a current of 100 mA. The salt bridge is 3g of agar dissolved in 97mL of water, and then 30g of KCl is added.
As shown in FIG. 3, the solutions contained in the reaction vessels were all acetonitrile solutions containing the compound represented by (Ib). Wherein, the left side diagram is the state before electrolysis, A represents a cathode, and B represents an anode; the acetonitrile solution containing the compound represented by (Ib) was colorless. The middle panel is the electrolytic process, a represents the cathode and B represents the anode, and it can be seen that during the electrolytic process, the acetonitrile solution containing the compound represented by (Ib) remained colorless at the anode, while the acetonitrile solution containing the compound represented by (Ib) turned red at the cathode. The right graph shows the results of the electrolysis after exchanging the anode and cathode, where A represents the anode and B represents the cathode, and during the electrolysis, it was found that the acetonitrile solution containing the compound represented by (Ib) gradually changed from colorless to red at the cathode, and the acetonitrile solution containing the compound represented by (Ib) gradually changed from red to colorless at the anode.
It can be seen that the electrochromic process of the compounds of the formula (Ib) is also a reversible process. The red color appears dark black in fig. 3 due to the drawing color.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A spiro-dipyrromethane having the structure shown in formula (I):
Figure FDA0001880244070000011
wherein R is1、R2、R3、R4、R5、R6Identical or different, independently of one another, from the group consisting of H, alkyl, -alkyl-COO-alkyl, -alkyl-OCO-alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heteroaryl, heteroaralkyl, amino, quaternary amine, nitro, nitrile, -SO3H、-CO-R8、-COO-R9、-CO-NR10R11A halogen; and said R is1、R2、R3、R4、R5、R6At least one of them is the following group: quaternary amine, nitro group, nitrile group, -SO3H、-CO-R8、-COO-R9、-CO-NR10R11Halogen, alkynyl; wherein R is8、R9、R10、R11The same or different, optionally H, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heteroaryl, heteroaralkyl;
R1’、R2’、R3’、R4' same or different, independently from each other, are selected from the group consisting of H, -alkyl-COO-alkyl, -alkyl-OCO-alkyl, amino, alkoxy, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, aryloxy, heteroaryl, heteroaralkyl;
R7is selected from- (NR)12) -, -O-; wherein R is12Selected from the group consisting of H, alkyl, amino, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heteroaryl, heteroaralkyl;
r is as defined above1、R2、R3、R4，R5、R6、R7、R1’、R2’、R3’、R4In the groups of the definition of' said alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heteroaryl, heteroaralkyl groups may be optionally substituted by one or more substituents, which may be the same or different, independently from each other selected from alkyl, alkoxy, halogen, nitro.
2. Spiro-dipyrromethane according to claim 1, wherein R is5、R6is-COO-alkyl or nitrile group.
The R is3、R4is-COO-alkyl or nitrile group.
The R is7is-O-or- (NR)12) -, wherein R12Selected from alkyl groups.
3. Spiro-dipyrromethane according to claim 1 or 2, wherein in the compound of formula (I), R is5、R6is-COO-alkyl, R7is-O-, R1、R2、R3、R4、R1’、R2’、R3’、R4' same or different, independently from each other, are selected from H, alkyl, -alkyl-COO-alkyl, -alkyl-OCO-alkyl, cycloalkyl; the alkyl or cycloalkyl groups may be further substituted by alkyl or halogen.
Preferably, in the compound represented by the formula (I), R3、R4is-CN, R7Is- (NR)12) -, wherein R12Selected from alkyl, R1、R2、R5、R6、R1’、R2’、R3’、R4' same or different, independently from each other, are selected from H, alkyl, -alkyl-COO-alkyl, -alkyl-OCO-alkyl, cycloalkyl; the alkyl or cycloalkyl groups may be further substituted by alkyl or halogen.
Preferably, said R is1’、R2’、R3’、R4' is H.
4. Spirocyclic-dipyrromethane according to any of claims 1 to 3, wherein the compound of formula (I) is selected from the following structures (Ia) and (Ib):
Figure FDA0001880244070000021
5. a process for the preparation of spiro-dipyrromethane according to any of claims 1 to 4, comprising the following steps:
Figure FDA0001880244070000031
wherein R is1、R2、R3、R4、R5、R6、R7、R1’、R2’、R3’、R4' as defined in any one of claims 1 to 4;
1) dissolving the compound of the general formula (1) and the compound of the general formula (2) in an organic solvent, mixing with the compound of the general formula (3), and reacting to obtain a compound of the general formula (4);
2) reacting the compound of the general formula (4) obtained in the step 1) with an oxidant to obtain the compound of the general formula (I).
6. The method according to claim 5, wherein in step 1), the reaction is preferably at room temperature and the reaction time is preferably 8-20 hours, such as 12 hours. The organic solvent is Dichloromethane (DCM), Tetrahydrofuran (THF) and acetonitrile (CH)3CN).
Preferably, the solution after the reaction in step 1) is poured into water, extracted with dichloromethane (preferably 3 times), the organic phase is washed with saturated aqueous sodium bicarbonate solution (preferably 2 times) and dried by spinning to give the compound of formula (4).
Preferably, the compound of the general formula (4) obtained above is purified by silica gel column chromatography, preferably using a mixed system of petroleum ether and ethyl acetate in a volume ratio of (1-5):1, for example 2:1 or 3: 1.
Preferably, in step 2), the organic solvent for the reaction is dichloromethane, tetrahydrofuran, acetonitrile, or the like.
Preferably, in step 2), the solution obtained after the reaction in step 1) or the purified compound of formula (4) is dissolved in an organic solvent, and mixed with an oxidizing agent for reaction.
Preferably, the oxidizing agent is selected from dichlorodicyanoquinone (DDQ) or Chloranil (chlorenil). The oxidizing agent is preferably added to the reaction system at a time.
Preferably, the compound of formula (I) obtained above is purified by silica gel column chromatography, preferably using ethyl acetate-petroleum ether 1 (5-9) developing system.
7. Dipyrromethene, the structure of which is shown as the following general formula (II):
Figure FDA0001880244070000041
wherein R is1、R2、R3、R4、R5、R6、R7、R1’、R2’、R3’、R4' is as defined in any one of claims 1 to 4.
Preferably, the compound of formula (II) is selected from the structures of formulae (IIa) and (IIb) below:
Figure FDA0001880244070000042
8. a process for preparing the dipyrromethene of claim 7, comprising dissolving the spiro-dipyrromethene of any one of claims 1 to 4 in an alkaline solution, or subjecting the spiro-dipyrromethene of any one of claims 1 to 4 to electrolysis:
Figure FDA0001880244070000051
9. use of a spiro-dipyrromethane according to any one of claims 1 to 4 or a dipyrromethene according to claim 7 for base-electrochromic devices.
10. Use of a spiro-dipyrromethane according to any one of claims 1 to 4 or a dipyrromethene according to claim 7 for electrochromic devices.
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