Structure and application of a class of 1,6-diyne compounds

Abstract

The present application discloses a 1,6-diyne compound, a compound represented by the general formula (I), and its tautomers, polymorphs, solvates, or salts thereof, a preparation method thereof, and applications thereof. The 1,6-diyne is a class of compounds with structural diversity, which can be used as an important compound to synthesize compounds with great application value in fluorescent materials.

Description

Technical Field

[0001] The present application belongs to the field of organic synthesis and relates to the structure of 1,6-diyne compounds and their application in the synthesis of large conjugated fused ring compounds. Background Art

[0002] Polycyclic condensed ring compounds are widely present in the fields of natural products, drugs and materials. Since polycyclic condensed ring compounds have large conjugated structures and relatively good luminescent properties, they are widely used in the field of luminescent materials. Therefore, the synthesis methods and application research of polycyclic condensed ring compounds have attracted much attention from organic synthetic chemists. At present, there are two main ways to prepare condensed ring compounds: 1. Further modification of existing cyclic compounds to obtain the required structure; 2. Using highly unsaturated compounds such as 1,n-ene yne, 1,n-diene, 1,n-diyne, etc., cyclization reactions occur under certain conditions to construct condensed ring compounds. The former has a higher purpose, but requires the substrate to be pre-designed and synthesized. The latter has higher efficiency and can construct multiple chemical bonds at the same time.

[0003] 1,6-Diyne compounds are a class of highly unsaturated compounds containing two carbon-carbon triple bonds. They can work synergistically during the reaction process and can undergo a variety of tandem cyclization reactions. They have a variety of reaction properties and can obtain cyclic compounds with different structures. The synthesis of 1,6-diyne compounds is simple. 1,6-diyne compounds with diverse structures can be synthesized through simple nucleophilic attack, substitution or coupling of alkyne molecules. Under the action of electrophilic reagents, transition metals or bases, 1,6-diyne can obtain structurally diverse fused ring compounds through different pathways. In other words, the structure of 1,6-diyne itself is diverse, and the products are also diverse under different reaction conditions. Therefore, 1,6-diyne is a very useful class of organic synthesis intermediates. Summary of the invention

[0004] According to one aspect of the present application, a 1,6-diyne compound is provided. The 1,6-diyne is a class of compounds with structural diversity, which can be used as an important compound to synthesize compounds with great application value in fluorescent materials.

[0005] A compound represented by general formula (I), and its tautomers, polymorphs, solvates, or salts thereof,

[0006]

[0007] wherein X is selected from nitrogen atom, phosphorus atom, arsenic atom, tellurium atom, and boron atom;

[0008] R' is selected from C 1 –C 30Alkyl, substituted C 1 –C 30 Alkyl, C 6 –C 30 Aryl, substituted C 6 –C 30 Aryl, C 3 –C 30 Heteroaryl, substituted C 3 –C 30 Heteroaryl, amino, substituted amino and optionally inserted at any position by a heteroatom group selected from the following: CO, O, S, SO, SO 2 NR a ,-N=,=N-;,

[0009] Among them, R 1a , R 4a independently selected from hydrogen, deuterium, C 1 –C 30 Alkyl, substituted C 1 –C 30 Alkyl, C 6 –C 30 Aryl, substituted C 6 –C 30 Aryl, C 3 –C 30 Heteroaryl, substituted C 3 –C 30 Heteroaryl, phosphino, substituted phosphino, boro, substituted boro, silicon, substituted silicon, halogen, amino, substituted amino, and optionally inserted at any position by a heteroatom group selected from the following: CO, O, S, SO, SO 2 NR a ,-N=,=N-;

[0010] R 2a Selected from C 6 –C 30 Aryl, substituted C 6 –C 30 Aryl, C 3 –C 30 Heteroaryl, substituted C 3 –C 30 Heteroaryl, C 1 –C 10 Alkenyl, C 1 –C 10 Substituted alkenyl,

[0011] R 3a For hydrogen, deuterium, C 1 –C 30 Alkyl, substituted C 1 –C 30 Alkyl, C1 –C 30 Alkenyl, substituted C 1 –C 30 Alkenyl, C 1 –C 30 Alkynyl, substituted C 1 –C 30 Alkynyl, C 6 –C 30 Aryl, substituted C 6 –C 30 Aryl, C 3 –C 30 Heteroaryl, substituted C 3 –C 30 Heteroaryl, C 1 –C 30 Cycloalkyl, substituted C 1 –C 30 Cycloalkyl, C 1 –C 30 Heterocycloalkyl, substituted C 1 –C 30 Heterocycloalkyl, phosphino, halogen, silicon, boron, germanium, arsenic, selenium and optionally inserted at any position by a heteroatom group selected from the following: CO, O, S, SO, SO 2 NR a ,-N=,=N-;

[0012] R a are independently selected from H, alkyl or aryl.

[0013] Optionally, substituted C 6 –C 30 Aryl, substituted C 3 –C 30 The substituents in the heteroaryl group are selected from alkyl, alkenyl, aldehyde, halogen, haloalkyl, alkyl inserted with an ester group, alkoxy, alkylthio, and substituted amino.

[0014] Optionally, substituted C 6 –C 30 Aryl, substituted C 3 –C 30 The substituents in the heteroaryl group are selected from C 1 –C 30 Alkyl, C 1 –C 30 Alkenyl, C 1 –C 30 Aldehyde, halogen, halogenated C 1 –C 30 Alkyl, ester inserted C 1 –C 30 Alkyl, C 1 –C 30Alkoxy, C 1 –C 30 Alkylthio, phenyl substituted amino.

[0015] Optionally, R' is selected from C 6 –C 30 Aryl, C 6 –C 10 Alkyl substituted C 6 –C 30 Aryl, "halogen-substituted C 6 –C 10 Alkyl" substituted C 6 –C 30 Aryl, C 3 –C 30 Heteroaryl, C 6 –C 10 Alkyl substituted C 3 –C 30 Heteroaryl, "halogen-substituted C 6 –C 10 Alkyl" substituted C 3 –C 30 heteroaryl;

[0016] Preferably, R' is selected from C 6 –C 30 Aryl, C 3 –C 30 Heteroaryl.

[0017] Optionally, R 1a , R 4a independently selected from hydrogen, aryl, alkyl substituted C 6 –C 30 Aryl, "S-inserted alkyl" substituted C 6 –C 30 Aryl, "O-inserted alkyl" substituted C 6 –C 30 Aryl, halogen substituted C 6 –C 30 Aryl, Aryl-substituted C 6 –C 30 Aryl, "halogen-substituted alkyl" substituted C 6 –C 30 Aryl, "aryl substituted amino" substituted C 6 –C 30 Aryl, "ester-inserted alkyl" substituted C 6 –C 30 Aryl, C 3 –C 30 heteroaryl;

[0018] Preferably, R1a are independently selected from phenyl, tert-butyl substituted phenyl, CH 3 S-substituted phenyl, CH 3 O-substituted phenyl, naphthyl, phenyl substituted with phenyl, phenyl substituted with at least one methyl group, CF 3 O-substituted phenyl, Br-substituted phenyl, "diphenyl-substituted amino" substituted phenyl, "ester-inserted methyl" substituted phenyl, dibenzothienyl.

[0019] Optionally, R 2a Selected from C 6 –C 30 Aryl, "ester-inserted alkyl" substituted C 6 –C 30 Aryl, alkyl substituted C 6 –C 30 Aryl, "oxygen-inserted alkyl" substituted C 6 –C 30 Aryl, Aryl-substituted C 6 –C 30 Aryl, C 3 –C 30 Heteroaryl, aldehyde substituted C 6 –C 30 Aryl, halogen substituted C 6 –C 30 Aryl, alkenyl substituted C 6 –C 30 Aryl;

[0020] Preferably, R 2a The group selected from phenyl, naphthyl, phenyl substituted with a "methyl group inserted into an ester group", phenyl substituted with a propyl group, phenanthrenyl, phenyl substituted with a "methyl group inserted into an oxygen atom", biphenyl, thienyl, phenyl substituted with a formaldehyde group, phenyl substituted with a Cl group, and phenyl substituted with a vinyl group.

[0021] Optionally, R 3a Selected from hydrogen atoms, deuterium atoms, C 6 –C 30 Aryl, "ester-inserted alkyl" substituted C 6 –C 30 Aryl, at least one alkyl substituted C 6 –C 30 Aryl;

[0022] Preferably, R 3a Selected from a hydrogen atom, a deuterium atom, a phenyl group, a phenyl group substituted with a "methyl group inserted with an ester group", and a phenyl group substituted with at least one methyl group.

[0023] Optionally, the tautomer has the general formula (II), (III) or (IV);

[0024] or or

[0025] According to another aspect of the present application, a method for preparing the compound described in any one of the above items is provided, comprising the following steps:

[0026] The raw materials containing the compounds represented by the general formula (V) and (VI) are reacted to obtain the compound represented by the general formula (I);

[0027]

[0028] Optionally, the molar ratio of the compounds represented by general formula (V) and (VI) is 1:1-5;

[0029] Preferably, the reaction is carried out in the presence of an acid reagent; the acid reagent includes p-toluenesulfonic acid, p-nitrobenzenesulfonic acid, methanesulfonic acid, ferric chloride, and aluminum chloride;

[0030] Preferably, the reaction temperature is 25-100° C.; the reaction time is 0.1-48 hours.

[0031] Optionally, the preparation method of the compound represented by general formula (V) comprises the following steps:

[0032] The raw materials containing the compounds represented by the general formula (VII) and (VIII) are reacted to obtain the compound represented by the general formula (V);

[0033]

[0034] Optionally, the molar ratio of the compounds represented by general formula (VII) and (VIII) is 1:1-5;

[0035] Preferably, the reaction is carried out in the presence of a nucleophilic substitution reagent; the nucleophilic substitution reagent includes n-butyl lithium, sec-butyl lithium, tert-butyl lithium, methyl lithium, lithium diisopropylamide, lithium bistrimethylsilylamide;

[0036] Preferably, the reaction temperature is -78-25°C; and the reaction time is 0.1-24 hours.

[0037] As an embodiment, the preparation method of the compound comprises the following steps:

[0038]

[0039] The main step is that alkynes perform nucleophilic substitution on aldehyde compounds to obtain propargyl alcohol compounds. The propargyl alcohol compounds are then coupled with N-propargyl sulfonamide compounds to synthesize the desired compounds.

[0040] According to another aspect of the present application, there is provided a use of any of the above compounds in the preparation of an isoindole dimer compound, wherein the isoindole dimer compound has a structure shown in the following formula:

[0041]

[0042] in,

[0043] X and Y are independently selected from nitrogen atoms, phosphorus atoms, arsenic atoms, tellurium atoms, and boron atoms;

[0044] R 1 , R 4 Same or Different; R 1 , R 4 are independently selected from hydrogen, C 1 –C 30 Alkyl, substituted C 1 –C 30 Alkyl, C 6 –C 30 Aryl, substituted C 6 –C 30 Aryl, C 3 –C 30 Heteroaryl, substituted C 3 –C 30 Heteroaryl, phosphino, substituted phosphino, boro, substituted boro, silicon, substituted silicon, halogen, amino, substituted amino, and optionally inserted at any position by a heteroatom group selected from the following: CO, O, S, SO, SO 2 NR a ,-N=,=N-;

[0045] R 2 , R 5 Same or Different; R 2 , R 5 Independently selected from C 6 –C 30 Aryl, substituted C 6 –C 30 Aryl, C 3 –C 30 Heteroaryl, substituted C 3 –C 30 heteroaryl;

[0046] R 3 , R 6 Same or Different; R 7 , R8 Same or Different; R 3 , R 6 , R 7 , R 8 are independently selected from hydrogen atoms, C 1 –C 30 Alkyl, substituted C 1 –C 30 Alkyl, C 1 –C 30 Alkenyl, substituted C 1 –C 30 Alkenyl, C 1 –C 30 Alkynyl, substituted C 1 –C 30 Alkynyl, C 6 –C 30 Aryl, substituted C 6 –C 30 Aryl, C 3 –C 30 Heteroaryl, substituted C 3 –C 30 Heteroaryl, C 1 –C 30 Cycloalkyl, substituted C 1 –C 30 Cycloalkyl, C 1 –C 30 Heterocycloalkyl, substituted C 1 –C 30 Heterocycloalkyl, phosphino, halogen, silicon, boron, germanium, arsenic, selenium and optionally inserted at any position by a heteroatom group selected from the following: CO, O, S, SO, SO 2 NR a ,-N=,=N-;

[0047] R a are independently selected from H, alkyl or aryl.

[0048] According to another aspect of the present application, there is provided a use of any of the above compounds in detecting substances containing active oxygen.

[0049] Optionally, the active oxygen includes at least one of sodium hypochlorite, hydrogen peroxide, and ozone.

[0050] Optionally, the compound of the general formula (I) is applied to a carrier such as a silica gel plate, a ceramic sheet, a polytetrafluoroethylene sheet, a sapphire substrate, a glass or a silicon dioxide substrate, and then a compound with active oxygen (sodium hypochlorite, hydrogen peroxide, ozone, etc.) is dripped onto the carrier. Then, the carrier is heated for 30 seconds. The carrier will change from colorless to red, and the fluorescence will gradually show strong fluorescence under irradiation of a 365nm ultraviolet lamp.

[0051] According to another aspect of the present application, there is provided a use of any of the above compounds in cell imaging.

[0052] In the present application, "alkyl" refers to a group obtained by losing a H atom from an alkane.

[0053] The term "alkenyl" refers to a group derived from an alkene group losing a hydrogen atom.

[0054] "Alkynyl" refers to a radical derived from an alkyne that loses a hydrogen atom.

[0055] The term "cycloalkyl" refers to a group derived from a cycloalkane that loses one hydrogen atom.

[0056] The term "heterocycloalkyl" refers to a group derived from a heterocycloalkane that has lost one hydrogen atom.

[0057] "Aryl" refers to a group formed by losing a hydrogen atom from an aromatic hydrocarbon.

[0058] "Heteroaryl" refers to a group derived from a heteroaromatic hydrocarbon losing a hydrogen atom.

[0059] "Substituted alkyl", "substituted aryl" and the like refer to alkyl substituted with any group and aryl substituted with any group, respectively.

[0060] "Heteroatom groups inserted at any position" means that heteroatom groups can be inserted into the group by replacing H atoms or C atoms, for example, "O atoms inserted into methyl groups are CH 3 O-", "S atoms inserted into methyl groups to form CH 3 S-", "NH inserts into methyl to form CH 3 NH-", "N atom inserted into phenyl group is pyridyl", etc.

[0061] "Alkyl-substituted aryl", "aryl-substituted aryl" and the like refer to aryl groups containing alkyl substituents and aryl groups containing aryl substituents, respectively. etc.; where “*” represents the connection point of the group.

[0062] In the present application, unless otherwise specified, "alkyl", "aryl" and the like may have any number of connection points; generally 1 connection point, 2 connection points, 3 connection points, 4 connection points or 5 connection points.

[0063] “C 1 –C 30 " is the average number of C atoms.

[0064] "Halogenated C 1 –C 30"Alkyl" and the like refer to alkyl groups having 1 to 30 carbon atoms substituted by halogen.

[0065] "Halogen" refers to fluorine, chlorine, bromine and iodine.

[0066] "Salt" refers to acidic and / or basic salts formed with inorganic and / or organic acids and bases. In addition, when the compounds of the present invention contain a basic moiety (such as, but not limited to, pyridine or imidazole) and an acidic moiety (such as, but not limited to, a carboxylic acid), zwitterions ("inner salts") may be formed and are included in the term "salt" as used herein.

[0067] "Solvate" includes, for example, hydrate.

[0068] The structural formula described in this application is intended to include all isomeric forms (such as enantiomers, diastereomers and geometric isomers (or conformational isomers)): for example, R-S configurations containing asymmetric centers, (Z), (E) isomers of double bonds, etc. Therefore, single stereochemical isomers of the compounds of this application or mixtures of their enantiomers, diastereomers or geometric isomers (or conformational isomers) all fall within the scope of this application.

[0069] "Tautomers" means that structural isomers with different energies can interconvert over a low energy barrier. For example, proton tautomers (i.e., prototropic tautomers) include interconversion via proton migration. Valence tautomers include interconversion via reorganization of some of the bonding electrons.

[0070] "Solvate" refers to a complex in which the compound of the present invention is coordinated with solvent molecules to form a specific ratio.

[0071] The beneficial effects of this application include:

[0072] 1) The 1,6-diyne compounds provided in the present application have variable structures, are convenient to synthesize, and are suitable for industrial production.

[0073] 2) The 1,6-diyne compounds provided in the present application are used to synthesize a class of benzisoindole dimer compounds and their derivatives.

[0074] 3) Use of the 1,6-diyne compounds provided in this application for cell imaging

[0075] 4) The 1,6-diyne compounds provided in the present application are used for detecting substances containing active oxygen (sodium hypochlorite, hydrogen peroxide, ozone, etc.). BRIEF DESCRIPTION OF THE DRAWINGS

[0076] Figure 1 It shows the color development of compound PA-1 under fluorescence. DETAILED DESCRIPTION

[0077] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0078] Unless otherwise specified, the raw materials and catalysts in the examples of this application were purchased through commercial channels.

[0079] The analysis method in the examples of this application is as follows:

[0080] NMR analysis was performed using Bruker AVANCE III HD 400 or JEOL ECZ600R.

[0081] UV-visible absorption and emission spectra were performed using Shimadzu UV-1900 and Edinburgh FS5-NIR.

[0082] The cyclic voltammetry curves were analyzed using Shanghai Chenhua electrochemical analyzer.

[0083] Example 1 Preparation of 1,6-diyne compounds

[0084] The compounds in Table 1 are prepared by the following method:

[0085]

[0086] Add phenylacetylene (5mmol, 1equiv.) and tetrahydrofuran 10mL to a dry 50mL round-bottom flask equipped with a stirrer. Cool the round-bottom flask to -78°C under an inert gas atmosphere and slowly add n-butyl lithium (2.5M inTHF, 2mL, 5mmol, 1equiv.). Return the reaction to room temperature and stir for 30 minutes, then cool to -78°C again. Dissolve benzaldehyde (5mmol, 1equiv.) in tetrahydrofuran and slowly add it dropwise to the reaction solution. After the addition is complete, return the reaction to room temperature and stir for 30 minutes. After the reaction is completed, quench the reaction with saturated ammonium chloride aqueous solution, and extract the aqueous phase three times with ethyl acetate. Combine the organic phases, dry them with magnesium sulfate, filter them, and spin dry them to obtain the crude product of propargyl alcohol.

[0087] The crude propargyl alcohol and N-propargylbenzenesulfonamide (6 mmol, 1.2 equiv.) were dissolved in 10 mL of dichloromethane under an inert gas atmosphere. TsOH·H 2 O (0.5mmol, 10mol%), and then the reaction was heated to reflux overnight. After the reaction was completed, NaHCO 3 The saturated aqueous solution was quenched, and the aqueous phase was extracted three times with ethyl acetate. The organic phases were combined, dried over magnesium sulfate, filtered, and spin-dried to obtain a crude product of propargyl alcohol. The crude product was chromatographed on a silica gel column to obtain MP-1 (yield 57%).

[0088] The preparation method of PA-2 compound is similar to that of PA-1, except that N-propargylbenzenesulfonamide is replaced with the following structure

[0089] The preparation method of the PA-3 compound is similar to that of the PA-1 compound, except that phenylacetylene is replaced by 4-methoxyphenylacetylene.

[0090] The preparation method of PA-4 compound is similar to that of PA-1, except that phenylacetylene is replaced by 4-chlorophenylacetylene and benzaldehyde is replaced by 4-decyloxybenzaldehyde.

[0091] The preparation method of PA-5 compound is similar to that of PA-1, except that N-propargylbenzenesulfonamide is replaced with the following structure

[0092] The preparation method of PA-6 compound is similar to that of PA-1, except that benzaldehyde is replaced by 4-phenylbenzaldehyde and N-propargylbenzenesulfonamide is replaced by the following structure

[0093] The preparation method of PA-7 compound is similar to that of PA-1, except that benzaldehyde is replaced by 2-naphthaldehyde and N-propargylbenzenesulfonamide is replaced by the following structure

[0094] The preparation method of PA-8 compound is similar to that of PA-1, except that benzaldehyde is replaced by 4-methoxyformaldehyde.

[0095] The preparation method of PA-9 compound is similar to that of PA-1, except that benzaldehyde is replaced by 4-methoxyformaldehyde and N-propargylbenzenesulfonamide is replaced by the following structure

[0096] The preparation method of the PA-10 compound is similar to that of the PA-1 compound, except that benzaldehyde is replaced by thiophene-2-carboxaldehyde.

[0097] The preparation method of the PA-11 compound is similar to that of the PA-1 compound, except that phenylacetylene is replaced by 4-formylphenylacetylene.

[0098] The preparation method of the PA-12 compound is similar to that of the PA-1 compound, except that benzaldehyde is replaced by 4-tert-butylbenzaldehyde.

[0099] The preparation method of the PA-13 compound is similar to that of the PA-1 compound, except that benzaldehyde is replaced by 4-methylthiobenzaldehyde.

[0100] The preparation method of the PA-14 compound is similar to that of the PA-1 compound, except that benzaldehyde is replaced by 4-bromobenzaldehyde.

[0101] The preparation method of the PA-15 compound is similar to that of the PA-1 compound, except that phenylacetylene is replaced by 4-phenylphenylacetylene.

[0102] The preparation method of the PA-16 compound is similar to that of the PA-1 compound, except that phenylacetylene is replaced by 2-naphthylacetylene.

[0103] The preparation method of PA-17 compound is similar to that of PA-1, except that benzaldehyde is replaced by 4-phenylbenzaldehyde.

[0104] The preparation method of the PA-18 compound is similar to that of the PA-1 compound, except that benzaldehyde is replaced by 2,6-dimethylbenzaldehyde.

[0105] The preparation method of PA-19 compound is similar to that of PA-1, except that benzaldehyde is replaced by 2,6-dimethylbenzaldehyde and N-propargylbenzenesulfonamide is replaced by the following structure

[0106] The preparation method of the PA-20 compound is similar to that of the PA-1 compound, except that benzaldehyde is replaced by 2-phenylbenzaldehyde.

[0107] The preparation method of the PA-21 compound is similar to that of the PA-1 compound, except that benzaldehyde is replaced by 4-phenylbenzaldehyde, and phenylacetylene is replaced by 4-propylphenylacetylene.

[0108] The preparation method of PA-22 compound is similar to that of PA-1, except that benzaldehyde is replaced by 4-methylthiobenzaldehyde and N-propargylbenzenesulfonamide is replaced by the following structure

[0109] The preparation method of PA-23 compound is similar to that of PA-1, except that N-propargylbenzenesulfonamide is replaced by the following structure

[0110] The preparation method of PA-24 compound is similar to that of PA-1, except that benzaldehyde is replaced by 2-phenylbenzaldehyde and N-propargylbenzenesulfonamide is replaced by the following structure

[0111] The preparation method of the PA-25 compound is similar to that of the PA-1 compound, except that phenylacetylene is replaced by 4-chlorophenylacetylene.

[0112] The preparation method of PA-26 compound is similar to that of PA-1, except that benzaldehyde is replaced by 1-naphthaldehyde.

[0113] The preparation method of PA-27 compound is similar to that of PA-1, except that N-propargylbenzenesulfonamide is replaced with the following structure

[0114] The preparation method of PA-28 compound is similar to that of PA-1, except that benzaldehyde is replaced by 4-decyloxyformaldehyde, phenylacetylene is replaced by 4-chlorophenylacetylene, and N-propargylbenzenesulfonamide is replaced by the following structure

[0115] The preparation method of the PA-29 compound is similar to that of the PA-1 compound, except that phenylacetylene is replaced by 4-propylphenylacetylene.

[0116] The preparation method of the PA-30 compound is similar to that of the PA-1 compound, except that phenylacetylene is replaced by 2-naphthylacetylene.

[0117] The preparation method of PA-31 compound is similar to that of PA-1, except that N-propargylbenzenesulfonamide is replaced with the following structure

[0118] The preparation method of PA-32 compound is similar to that of PA-1, except that benzaldehyde is replaced by 4-methoxybenzaldehyde and N-propargylbenzenesulfonamide is replaced by the following structure

[0119] The preparation method of the PA-33 compound is similar to that of the PA-1 compound, except that phenylacetylene is replaced by 4-methoxycarbonylphenylacetylene.

[0120] The preparation method of the PA-34 compound is similar to that of the PA-1 compound, except that phenylacetylene is replaced by 9-ethynylphenanthrene.

[0121] The preparation method of the PA-35 compound is similar to that of the PA-1 compound, except that benzaldehyde is replaced by 4-diphenylaminobenzaldehyde.

[0122] The preparation method of PA-36 compound is similar to that of PA-1, except that N-propargylbenzenesulfonamide is replaced with the following structure

[0123] The preparation method of the PA-37 compound is similar to that of the PA-1 compound, except that benzaldehyde is replaced by 4-formyldibenzothiophene.

[0124] The preparation method of PA-38 compound is similar to that of PA-1, except that benzaldehyde is replaced by 4-trifluoromethylbenzaldehyde.

[0125] The preparation method of the PA-39 compound is similar to that of the PA-1 compound, except that benzaldehyde is replaced by 4-vinylbenzaldehyde.

[0126] The preparation method of the PA-40 compound is similar to that of PA-1, except that phenylacetylene is replaced by 2,3,4,5,6-pentadeuterated phenylacetylene.

[0127] Table 1

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136] Example 2 Compound PA-1 is used to synthesize a class of benzisoindole dimer compounds and their derivatives

[0137]

[0138] Compound PA-1 (385 mg, 1 mmol) and 650 mg of cesium carbonate were added to a reaction tube, and oxygen was introduced. Toluene was then added as a solvent. After 96 hours of reaction, the reaction solution was dried and passed through a column to obtain compound FL-1 (120 mg, yield 50%).

[0139] The NMR data of the product FL-1 are as follows:

[0140] 1 H NMR (400 MHz, CDCl 3 )δ9.49(s,2H),8.43(d,J=6.9Hz,4H),8.36(s,2H),8.12(d,J=7.8Hz,2H),7.99(d,J=7.8Hz,2H),7.72–7.65(m,6H),7.61–7.55(m,4H).

[0141] Example 3 Compound PA-23 is used to synthesize a class of benzisoindole dimer compounds and their derivatives

[0142]

[0143] Compound PA-23 (461 mg, 1 mmol), 276 mg potassium carbonate, and 1 mL of 8% sodium hypochlorite aqueous solution were added to the reaction tube. Isopropanol was then added as a solvent. After 96 hours of reaction, the reaction solution was dried and passed through a column to obtain compound FL-23 (120 mg, yield 38%).

[0144] The NMR test data of the product are as follows:

[0145] 1 H NMR (400 MHz, CDCl 3 )δ8.17(s,2H),8.02(d,J=8.4Hz,2H),7.92(d,J=7.8Hz,2H),7.80(dd,J=6.3, 2.8Hz,4H),7.67(d,J=7.3Hz,4H),7.53–7.40(m,14H),7.27(d,J=7.3Hz,2H). 13 C NMR (101 MHz, CDCl 3 )δ165.72,150.41,140.33,139.27,136.32,134.80,134.43,133.56,132.94,13 1.06,130.20,129.90,129.24,128.34,128.20,127.65,127.45,126.81,122.99.

[0146] Example 4 Use of PA-1 to PA40 for detecting active oxygen (sodium hypochlorite, hydrogen peroxide, ozone, etc.)

[0147] The compound PA-1 was dissolved in dichloromethane and applied to five polytetrafluoroethylene carriers, and then different concentrations of sodium hypochlorite aqueous solutions (8% mass concentration sodium hypochlorite aqueous solution, 50 times diluted solution, 500 times diluted solution, 500 times diluted solution, no NaClO aqueous solution) were dripped on the carriers. Then heated at 100°C for 30 seconds. The carrier will change from colorless to red, and the fluorescence will gradually show strong fluorescence under 365nm ultraviolet light.

[0148] Typical test results are as follows: Figure 1 As shown, Figure 1 It shows the color development of compound PA-1 under fluorescence.

[0149] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A 1,6-diyne compound, characterized in that: The 1,6-diyne compound is selected from at least one of the following compounds; 。 2. A method for preparing the 1,6-diyne compound according to claim 1, characterized in that: The following steps are involved: The raw materials containing the compounds represented by the general formula (V) and (VI) are reacted to obtain the 1,6-diyne compound; 。 3. The preparation method according to claim 2, characterized in that: The molar ratio of the compounds represented by general formula (V) and (VI) is 1:1-5.

4. The preparation method according to claim 2, characterized in that: The reaction is carried out in the presence of an acid reagent; the acid reagent comprises at least one of p-toluenesulfonic acid, phenylsulfonic acid, p-nitrobenzenesulfonic acid, methanesulfonic acid, ferric chloride and aluminum chloride.

5. The preparation method according to claim 2, characterized in that: The reaction temperature is 25-100° C. and the reaction time is 0.1-48 hours.

6. The preparation method according to claim 2, characterized in that: The preparation method of the compound represented by general formula (V) comprises the following steps: The raw materials containing the compounds represented by the general formula (VII) and (VIII) are reacted to obtain the compound represented by the general formula (V); 。 7. The preparation method according to claim 6, characterized in that: The molar ratio of the compounds represented by the general formula (VII) and (VIII) is 1:1-5.

8. The preparation method according to claim 6, characterized in that: The reaction is carried out in the presence of a nucleophilic substitution reagent; the nucleophilic substitution reagent includes at least one of n-butyl lithium, sec-butyl lithium, tert-butyl lithium, methyl lithium, diisopropyl lithium amide, and bistrimethylsilyl lithium amide.

9. The preparation method according to claim 6, characterized in that: The reaction temperature is -78 to 50°C; the reaction time is 0.1 to 24 hours.

10. Use of the 1,6-diyne compound according to claim 1 or the 1,6-diyne compound prepared by the method according to any one of claims 2 to 9 in the preparation of an isoindole dimer compound, characterized in that: The isoindole dimer compound has one of the structures shown in the following formula: 、 。 11. Use of the compound according to claim 1 or the compound prepared by the method according to any one of claims 2 to 9 in detecting substances containing active oxygen, characterized in that: The applications are non-diagnostic or therapeutic applications.

12. The use according to claim 11, characterized in that: The active oxygen includes at least one of sodium hypochlorite, hydrogen peroxide and ozone.

13. Use of the compound according to claim 1 or the compound prepared by the method according to any one of claims 2 to 9 in the preparation of a cell imaging agent.

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