CN108659018B - Crystal structure of ethyl-linked unsaturated demethylcantharidimide dimer, preparation method and application - Google Patents
Crystal structure of ethyl-linked unsaturated demethylcantharidimide dimer, preparation method and application Download PDFInfo
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Abstract
The invention relates to a crystal structure, a preparation method and partial properties of an unsaturated demethylcantharidimide dimer connected by ethyl. The crystal is white small block crystal with melting point of 184.4-184.9 deg.C and molecular formula C18H16N2O6Molecular weight 356.33, chemical name: 2,2' - (ethane-1, 2-diyl) bis (3a,4,7,7 a-tetrahydro-4, 7-epoxy-1, 3-dihydroisoindole-1, 3-dione), designated by the english system: 2,2' - (1,2-ethanediyl) bis [3a,4,7,7a-te-trahydro-4,7-epoxy-1,3-bishydroisoindole-1,3-dione]The structure is as follows:
. The analysis of the single crystal structure shows that the crystal is a triclinic crystal system,P ‑1space group, a =8.239(4) Å, b =10.295(5) Å, c =10.351(5) Å =96.549(5) °, β =107.849(6) °, γ =103.068(6) °, V =798.0 (6) Å3And Z = 2. The cantharidimide derivative crystal is simple in preparation method and has strong fluorescence emission between 300 and 400 nm. The cantharidimide derivative has certain application value in the aspect of pesticides for preventing and controlling diamondback moth larvae.
Description
Technical Field
The invention relates to the fields of fluorescent materials, pesticide chemistry and crystallography, in particular to a crystal structure of unsaturated demethylation cantharidimide dimer, a preparation method and application in the fields of fluorescent materials and pesticide chemistry.
Background
Cantharidin is an effective component of the traditional Chinese natural medicament cantharidin, can break primary and secondary DNA structures of cancer cells and further enable the cancer cells to be programmed to die, but the cantharidin is extremely toxic and difficult to synthesize, so that the clinical application of the cantharidin is limited. The demethyl cantharidin imide derivative not only retains the antitumor activity of demethyl cantharidin, but also has the characteristics of changeable structure, easy modification, coordination with metal and the like, and anticancer drug molecules with low toxicity and high activity can be obtained through structural modification; on the other hand, a dimer structure widely existing in natural products is generally recognized to have a better biological activity than a corresponding monomer structure, and drug molecules having the dimer structure have been synthesized in a large amount and used for treating cancer, aids, alzheimer's disease, malaria and various parasitic diseases. However, the types of the cantharidinimide-based dimers are very few, no more than ten types of the cantharidinimide-based dimers are reported in various literatures, the types of the unsaturated demethyl cantharidinimide-based dimers are fewer, and the reports on the crystal structures of the compounds are more rare; the applicant subject group has been engaged in the research of cantharidin derivatives in the field of anticancer drugs for many years, and recently found that such derivatives have special applications in the fields of fluorescent materials and pesticide chemistry.
The organic fluorescent materials are various in types, mostly have conjugated heterocycles and various chromophores, the structures are easy to adjust, and the conjugated length of the organic fluorescent materials is changed by introducing unsaturated groups such as olefinic bonds, benzene rings and the like and various chromophores, so that the photoelectric properties of the compounds are changed. Such as oxadiazole and derivatives thereof, triazole and derivatives thereof, rhodamine and derivatives thereof, coumarin derivatives, 1, 8-naphthalimide derivatives, pyrazoline derivatives, triphenylamine derivatives, porphyrin compounds, carbazole, pyrazine, thiazole derivatives, perylene derivatives and the like. They are widely used in the fields of optical electronic devices, DNA diagnosis, photochemical sensors, organic pigments, dyes, fluorescent whitening agents, photo-oxidants, fluorescent coatings, laser dyes, organic electroluminescent devices (ELD) chemical and biochemical analysis, solar traps, anti-counterfeiting marks, drug tracing, lasers and the like. However, no fluorescent material using unsaturated demethylcantharidimide dimer as a skeleton has been reported.
Cantharidin has been rarely studied for pesticides, and in 1974 James e, Carrel and Thomas Eisner, written in Science, at 10-5mol.L-1At very low concentrations, cantharidin has antifeedant effects against a variety of insects. In addition, it also has stomach toxicity, contact killing, and systemic effects. Cantharidin has wide insecticidal spectrum, has strong effect on lepidoptera and homoptera insects, and has obvious inhibition effect on various plant pathogenic fungi. Chenyong et al found that norcantharidin is similar to cantharidin, and has strong stomach toxicity and non-selective antifeedant effect on diamondback moth larvae. However, the toxic activity of norcantharidin is weaker than that of cantharidin, and a good toxic effect can be achieved by increasing the using dosage or adding a synergist. The research of the unsaturated demethyl cantharidimide on the pesticide is not reported, and the research of the dimer thereof on the field of the pesticide is not reported.
Disclosure of Invention
Structural characterization
The invention relates to a method for preparing a compound with two methylene groups (namely- (CH)2)2-) is a linked unsaturated demethylcantharidimide dimer crystal, the structure and related parameters of which are as follows:
the crystal is white small block crystal with melting point of 184.4-184.9 deg.C and molecular formula C18H16N2O6Molecular weight 356.33, chemical name: 2,2' - (ethane-1, 2-diyl) bis (3a,4,7,7 a-tetrahydro-4, 7-epoxy-1H-isoindole-1,3(2H) -dione), designated by the english system: 2,2' - (1,2-ethanediyl) bis [3a,4,7,7a-te-trahydro-4,7-epoxy-1H-isoindole-1,3(2H) -dione]The structure is as follows:
elemental analysis showed that the dimer C, H, N was present in 60.72%, 4.65% and 7.98% percent (according to formula C)18H16N2O6Calculated theoretical values are 60.67%, 4.53% and 7.86%, respectively); the analysis of the single crystal structure shows that the crystal is a triclinic crystal system,P -1space group, a =8.239(4) Å, b =10.295(5) Å, c =10.351(5) Å =96.549(5) °, β =107.849(6) °, γ =103.068(6) °, V =798.0 (6) Å3Z =2, related1HNMR spectrum,13The CNMR spectra are shown in figure 1 and figure 2 respectively; FIG. 3 and FIG. 4 are a thermal ellipsoid crystal structure diagram and a crystal structure stacking diagram of the compound, respectively.
Synthesis method
The dimer crystal has three synthetic methods: the first method takes unsaturated demethyl cantharidin and ethylenediamine as raw materials and comprises the following steps:
respectively dissolving unsaturated demethylcantharidin and ethylenediamine in a proper organic solvent, mixing according to a certain substance amount ratio, stirring and reacting at a certain temperature for a certain time to obtain a white powdery solid, volatilizing the concentrated solution, filtering, washing the powdery solid with a proper solvent, and then recrystallizing by a proper solvent to obtain a white small blocky crystal, namely a target product crystal; or directly mixing the two raw materials according to a certain mass ratio without using a reaction solvent to obtain a paste, grinding at normal temperature, and recrystallizing the obtained solid with a proper solvent to obtain the target product.
The second method takes unsaturated demethyl cantharidimide and 1, 2-dibromoethane as raw materials and comprises the following steps:
dissolving unsaturated demethyl cantharidimide and 1, 2-dibromoethane in a proper organic solvent, mixing according to a certain substance amount ratio, stirring and reacting at a certain temperature for a certain time to obtain a white small blocky solid, volatilizing and concentrating the solution, filtering, washing the powdery solid with a proper solvent, and then recrystallizing through a proper solvent to obtain a white small blocky crystal, namely a target product crystal; or directly mixing the two raw materials according to a certain mass ratio without using a reaction solvent to obtain a paste, grinding at normal temperature, and recrystallizing the obtained solid with a proper solvent to obtain the target product.
In the third method, furan and 1, 1' - (ethane-1, 2-diyl) -di (1H-pyrrole-2, 5-dione) are used as raw materials, and the steps are as follows:
dissolving 1, 1' - (ethane-1, 2-diyl) -bis (1H-pyrrole-2, 5-dione) in a proper organic solvent, adding furan according to a certain substance amount ratio, stirring for reaction or standing for a certain time at a certain temperature to obtain a white powdery solid, volatilizing the concentrated solution, filtering, washing the powdery solid with a proper solvent, and recrystallizing by using a proper solvent to obtain a white small blocky crystal, namely a target product crystal; or directly mixing the two raw materials according to a certain mass ratio without using a reaction solvent to obtain a paste, grinding at normal temperature, and recrystallizing the obtained solid with a proper solvent to obtain the target product.
The three above processes differ in the reactants, but the molar ratio of the reactants is between 4:1 and 1: 2.
The organic solvent (including solvent for reaction, washing and recrystallization) in the above three methods is selected from: methanol, ethanol, acetonitrile, dichloromethane, chloroform, tetrahydrofuran, ethyl acetate, toluene, acetone, N-Dimethylformamide (DMF), and the like; no solvent is used in the solid phase reaction, only a solvent is used in the recrystallization process.
Preferably, the reaction temperature and the recrystallization temperature are normal temperature or heating, the reaction method is stirring or standing, and the recrystallization method is natural volatilization in a standing state.
Preferably, the reaction time and recrystallization time are selected from: 2 hours to 3 days.
The invention has the beneficial effects that: relatively complex fluorescent materials can be synthesized in relatively simple steps and reactants.
Ultraviolet and fluorescent properties.
At 10-5The ultraviolet spectrum of the compound is tested in a mol/L ethanol solution, and the compound is found to have an ultraviolet absorption peak near 206nm (shown in figure 5).
Is also at 10-5In mol/L ethanol solution, ultraviolet light with the wavelength of 296nm is used for excitation, the fluorescence property of the compound is tested, strong fluorescence emission is found between 300 nm and 400nm, and the fluorescence spectrum is shown in figure 6.
Theoretical calculation results of ultraviolet spectrum
To explain the mechanism of generation of ultraviolet spectrum, we calculated the ultraviolet spectrum of the compound under b3lyp/6-311+ g (d, p)/cpcm method/base group by using TD-DFT theory with the help of Gaussian 03 software, and calculated as the same solvent condition as the solvent used in the experiment; the results are shown in FIG. 7 and it can be seen that the calculated UV spectrum has a major absorption peak at 204.5nm, which is shown by orbital analysis to be a pi → pi transition and nNThe result of the interaction of the → transition.
Experiments on disinsection
The method comprises the steps of taking diamondback moth larvae as an experimental object for insecticidal experiments, testing by using a 75% ethanol solution, measuring the comprehensive toxicity of the compound to the diamondback moth larvae by using an insect soaking method, predicting the lowest full lethal concentration and the highest full survival concentration of the diamondback moth larvae according to a preliminary experiment, setting 5-7 gradient concentrations within the range, soaking 3-year-old diamondback moth larvae into the liquid medicine with each concentration for 5 seconds, then placing the larvae on absorbent paper to absorb the redundant liquid medicine on the larvae, placing the larvae into a cylindrical bottle (the diameter is 3.5cm, and the height is 7.5 cm) paved with moisturizing filter paper, soaking cabbage leaves (the size is about 2cm × cm) in the liquid medicine for 2-3 seconds, absorbing the redundant liquid medicine, placing the larvae into the cylindrical bottle for feeding, treating 10 larvae each time, repeating each concentration gradient for three times, treating with clear water as a control, placing each treatment into a climatic incubator, controlling the humidity to be about 25 ℃, controlling the relative humidity to be 75% in a photoperiod 14/10(L/D), examining the death condition after 24 hours, and counting the death condition according to obtain the toxicity value of the compound, and obtaining an LC concentration equation of the larvae which is about 83 mg.
Detailed description of the preferred embodiments.
In order to better understand the present invention, the following three specific examples further illustrate the technical solution of the present invention.
Example 1.
Weighing 3.32g of unsaturated norcantharidin (0.02 mol) and dissolving in 50mL of toluene, stirring vigorously, adding 0.810mL (0.01 mol) of 1, 2-ethylenediamine, stirring at normal temperature for 24h to obtain white suspension, volatilizing the solvent to obtain residual 10mL, filtering, washing the precipitate with dichloromethane, and recrystallizing with methanol to obtain white small blocky crystals, namely the target product.
Example 2.
Dissolving 0.33g of unsaturated demethyl cantharidimide in 30ml of acetone, adding 0.19g of 1, 2-dibromoethane according to the mass ratio of 2:1, stirring at normal temperature for 24h to obtain white suspension, volatilizing the solvent to leave about 10ml, filtering, washing the precipitate with dichloromethane, and then recrystallizing with methanol to obtain white small blocky crystals, namely the target product.
Example 3.
0.22g of 1, 1' - (ethane-1, 2-diyl) -bis (1H-pyrrole-2, 5-dione) is dissolved in 50ml of toluene, 0.20g of furan is added in a mass ratio of 1:2, the mixture is heated under reflux for 10 hours, the solution is concentrated to 20ml, the solution is filtered, the precipitate is washed with dichloromethane, and then the precipitate is recrystallized with methanol, so that white small blocky crystals, namely the target product, can be obtained.
Description of the drawings.
FIG. 1 is a drawing of a target compound1H NMR spectrum.
FIG. 2 is a drawing of a target compound13CNMR spectrogram.
FIG. 3 is a crystal structure diagram of the objective compound with an ellipsoid probability of 30%.
FIG. 4 is a packing diagram of the crystal structure of the target compound.
FIG. 5 is a UV-Vis spectrum of the target compound.
FIG. 6 is a fluorescence spectrum of a target compound.
FIG. 7 is a graph of UV-Vis spectra of target compounds calculated using TD-DFT theory.
Claims (3)
1. An ethyl-linked unsaturated demethyl cantharidimide dimer crystal with white small crystal form, melting point of 184.4-184.9 deg.C, and molecular formula C18H16N2O6Molecular weight 356.33, chemical name: 2,2' - (ethane-1, 2-diyl) bis (3a,4,7,7 a-tetrahydro-4, 7-epoxy-1, 3-dihydroisoindole-1, 3-dione), designated by the english system: 2,2' - (1,2-ethanediyl) bis [3a,4,7,7a-te-trahydro-4,7-epoxy-1,3-bishydroisoindole-1,3-dione]The structure is as follows:
the single crystal structure analysis shows that the crystal is a triclinic system, P-1 space group, a =8.239(4) Å, b =10.295(5) Å, c =10.351(5) Å =96.549(5) °, β =107.849(6) °, gamma =103.068(6) °, V =798.0 (6) Å3，Z=2。
2. The process for preparing the unsaturated norcantharidinimide dimer crystal as claimed in claim 1, wherein: two reactants are taken as raw materials, and a one-step reaction is carried out in a proper organic solvent, or the reaction can be directly completed by the two raw materials without using the solvent, and the steps are as follows:
1) respectively dissolving the raw materials 1 and 2 in a proper organic solvent, mixing according to the mass ratio of 4:1 to 1:2, stirring and reacting for 2 hours to 3 days at normal temperature or under heating to obtain a white powdery solid which is a target product crude product, or directly mixing and reacting the two raw materials without using the organic solvent to obtain the crude product;
2) volatilizing the concentrated solution, filtering, washing the white powdery solid with a proper solvent, and then recrystallizing by a proper solvent to obtain white small blocky crystals, namely the target product crystals; if an organic solvent is not used, the step of volatilization and concentration can be saved, and the recrystallization operation is directly carried out on the crude product;
in the above method for producing a crystal of a compound, the two reactant materials are selected from: unsaturated demethylcantharidin and ethylenediamine, or unsaturated demethylcantharidinimide and 1, 2-dibromoethane, or furan and 1, 1' - (ethane-1, 2-diyl) -bis (1H-pyrrole-2, 5-dione);
in the above method for producing a crystal of a compound, the reaction solvent and the recrystallization solvent are selected from: methanol, ethanol, acetonitrile, dichloromethane, chloroform, tetrahydrofuran, ethyl acetate, toluene, acetone and N, N-dimethylformamide.
3. Use of a compound according to claim 1 or an agriculturally pharmaceutically acceptable salt thereof in the preparation of a pesticide for controlling diamondback moth larvae.
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| Synthesis, crystal structure, spectroscopic properties and potential anti-cancerous activities of four unsaturated bis-norcantharimides;Shuang-Shuang Cheng，等;《Journal of Molecular Structure》;20160227;第1115卷;第228-240页，第230页Scheme 3化合物4 * |
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