CN107176961B - The preparation and use of diethylenetriamine chain demethyl Chinese blister beetle acid imide dimer - Google Patents
The preparation and use of diethylenetriamine chain demethyl Chinese blister beetle acid imide dimer Download PDFInfo
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Abstract
The present invention relates to a kind of Chinese blister beetle acid imide dimer compound of diethylenetriamine chain link, the powdered crystal grain of compound white in appearance, 158.1-158.7 DEG C of fusing point, molecular formula C20H25N3O6, structure is as follows:
Description
Technical field:
The present invention relates to fluorescent material and field of pesticide chemistry, specially a kind of system of demethyl Chinese blister beetle acid imide dimer
Preparation Method and in fluorescent material and the purposes of field of pesticide chemistry.
Background technique:
Cantharidin is the effective component of Chinese tradition natural drug Chinese blister beetle, can make the DNA firsts and seconds knot of cancer cell
Structure fracture, and then cancer cell is made to enter programmed death, but cantharidin severe toxicity, synthesis is difficult, limits its clinical application.Go first
Base Chinese blister beetle imide derivative had not only remained the anti-tumor activity of cantharidin, but also had that structure is changeable, be easy to modify, can
The features such as being coordinated with metal is expected to obtain the anti-tumor drug molecule that toxicity is low, activity is high by structure of modification；On the other hand, exist
The dimeric structure being widely present in natural products is generally considered have bioactivity more better than corresponding monomer structure, tool
There is the drug molecule of dimeric structure largely to be synthesized, and for treating cancer, AIDS, Alzheimer disease, malaria and
Various parasitic diseases.But it is considerably less based on the imido dimeric species of Chinese blister beetle, it is seen in reported in the literature is no more than ten at present
Kind；Applicant seminar always works on cantharidin derivative in the research in anticancer drug field, it has recently found that such spread out for many years
Biology also has special purposes in fluorescent material and field of pesticide chemistry.
Organic fluorescence materials are many kinds of, they have conjugation heterocycle more and various chromophores, structure are easy to adjust, pass through
The unsaturated groups such as ethylene linkage, phenyl ring and various chromophores are introduced to change its conjugate length, so that compound optoelectronic property be made to send out
Changing.Such as oxadiazoles and its derivative species, triazole and its derivative species, rhodamine and its derivative species, Coumarins are derivative
Object, 1,8- naphthalimide analog derivative, pyrazoline derivative, triphen amine derivant, porphyrins, carbazole, pyrazine, thiophene
Azole derivative, analog derivative etc..They are widely used in optical electron device, DNA diagnosis, Optochemical sensor, organic
Pigment, dyestuff, fluorescent whitening agent, photooxidant, fluorescent paint, laser dye, organic electroluminescence device (ELD) chemistry and life
Change the fields such as analysis, solar energy trap, anti-fake mark, pharmaceutical indications and laser.But with demethyl Chinese blister beetle acid imide dimerization
Body is that the fluorescent material of skeleton has not been reported.
Research of the cantharidin for pesticide is seldom, and 1974, James E.Carrel and Thomas Eisner existed
It writes articles and points out on Science, 10-5mol.L-1Extremely low concentration under, cantharidin has Antifeedant Effects to various insects.In addition, also
Have stomach toxicity, tag, interior suction the effects of.The insecticidal spectrum of cantharidin is wider, with stronger to Lepidoptera, Homoptera insect effect, simultaneously
There is apparent inhibiting effect to various plants disease fungus.The discovery such as Chen Yong, Norcantharidin and cantharidin are seemingly, young to diamond-back moth
Worm equally has stronger stomach toxicity and non-selective Antifeedant Effects.But the cytotoxicity of Norcantharidin will be weaker than cantharidin, lead to
Crossing increasing dosage or synergist is added also can achieve good toxic effect.Demethyl Chinese blister beetle acid imide dimer is used for
The research of pesticide has not been reported.
Summary of the invention
1, structural characterization
The contents of the present invention are one kind to be prepared by a variety of methods with diethylenetriamine base (i.e.-(CH2-CH2-NH-
CH2-CH2) -) is the demethyl Chinese blister beetle acid imide dimer of connection chain, and the structure of the dimer and related characterization parameter are as follows:
The powdered crystal grain of compound white in appearance, 158.1-158.7 DEG C of fusing point, molecular formula C20H25N3O6, molecular weight
It is 403.43, chemical name are as follows: 2,2'- (3- aza-pentane -1,5- diyl) two [hexahydro -4,7- epoxy -1H- iso-indoles -1,3
(2H)-diketone], english system name are as follows: 2,2'- (3-aza-1,5-pentanediyl) bis [hexahydro-4,7-
Epoxy-1H-isoindole-1,3 (2H)-dione], structure is as follows:
Elemental analysis shows that the percentage composition of the dimer C, H, N are respectively 59.63%, 6.41% and 10.61% (to press
Molecular formula C22H28N2O6The theoretical value of calculating is respectively 59.54%, 6.25% and 10.42%)；Pass through1HNMR and13CNMR nuclear-magnetism
Resonance method characterizes its structure, sees attached drawing 1 and attached drawing 2 respectively in relation to spectrogram.
2, synthetic method
There are five types of synthetic methods for the dimer: method is first is that be original with unsaturated cantharidin and diethylenetriamine
Material, steps are as follows:
After unsaturated cantharidin and diethylenetriamine are dissolved in suitable organic solvent respectively, according to certain object
The mixing of the ratio between amount of matter, is stirred to react certain time at a certain temperature, obtains pale yellow powder shape solid, and volatilization concentration is molten
Liquid, filtering, pulverulent solids are washed with suitable solvent, are then recrystallized by suitable solvent, obtain colourless rhabdolith A,
Its ingredient is 2,2'- (3- aza-pentane -1,5- diyl) two (3a, 4,7,7a- tetrahydro -4,7- epoxy -1H- iso-indoles -1,3
(2H)-diketone)；It takes the crystal to be dissolved in suitable organic solvent, a certain amount of palladium-carbon catalyst is added, is passed through hydrogen, certain
At a temperature of be stirred to react certain time, filter, stand volatilization, after a few days, the white powder crystal being precipitated in solution is target product
Crystal；It can also not have to reaction dissolvent in the step for preparing colourless rhabdolith A, two kinds of raw materials are directly pressed certain substance
The mixing of the ratio between amount, griding reaction under room temperature, obtained solid recrystallizes with suitable solvent, also available crystal A.
Method is second is that amine is raw material using unsaturated demethyl Chinese blister beetle acid imide and two (2- bromoethyls), and steps are as follows:
After unsaturated demethyl Chinese blister beetle acid imide and two (2- bromoethyl) amine are dissolved in suitable organic solvent, according to certain
The mixing of the ratio between the amount of substance, be stirred to react certain time at a certain temperature, obtain pale yellow powder shape solid, volatilization concentration
Solution, filtering, pulverulent solids are washed with suitable solvent, are then recrystallized by suitable solvent, obtain colourless rhabdolith
A, ingredient 2,2'- (3- aza-pentane -1,5- diyl) two (3a, 4,7,7a- tetrahydro -4,7- epoxy -1H- iso-indoles -1,3
(2H)-diketone)；It takes the crystal to be dissolved in suitable organic solvent, a certain amount of palladium-carbon catalyst is added, is passed through hydrogen, certain
At a temperature of be stirred to react certain time, filter, stand volatilization, after a few days, the white powder crystal being precipitated in solution is target product
Crystal；It can also not have to reaction dissolvent in the step for preparing colourless rhabdolith A, two kinds of raw materials are directly pressed certain substance
The mixing of the ratio between amount, griding reaction under room temperature, obtained solid recrystallizes with suitable solvent, also available crystal A.
Method third is that with furans and 1,1'- (2,2'- azepine dialkyl group two (ethane -2,1- diyl)) two (1H- pyrroles -2,
5- diketone) it is raw material, steps are as follows:
1,1'- (2,2'- azepine dialkyl group two (ethane -2,1- diyl)) two (1H- pyrrole-2,5-diones) are dissolved in properly
Organic solvent after, according to the ratio between certain amount of substance be added furans, be stirred to react or stand at a certain temperature one periodically
Between, pale yellow powder shape solid is obtained, concentrate solution of volatilizing filters, and pulverulent solids are washed with suitable solvent, then passed through
Suitable solvent recrystallization, obtains colourless rhabdolith A, ingredient 2,2'- (3- aza-pentane -1,5- diyl) two (3a, 4,7,
- 1,3 (2H)-diketone of 7a- tetrahydro -4,7- epoxy -1H- iso-indoles)；It takes the crystal to be dissolved in suitable organic solvent, is added certain
The palladium-carbon catalyst of amount is passed through hydrogen, is stirred to react certain time at a certain temperature, filtering, stands volatilization, after a few days, molten
The white powder crystal being precipitated in liquid is target product crystal；Reaction can also not be had in the step for preparing colourless rhabdolith A
Solvent is directly mixed two kinds of raw materials by the ratio between certain amount of substance, griding reaction under room temperature, and obtained solid is used suitable molten
Agent recrystallizes, also available crystal A.
Method one, method two and method three are two-step reaction, their difference is that reactant is different, but reactant
Molar ratio is between 4:1 and 1:2.
Method is fourth is that using cantharidin and diethylenetriamine as raw material, and steps are as follows:
After cantharidin and diethylenetriamine are dissolved in suitable organic solvent respectively, according to the amount of certain substance
The ratio between mixing, be stirred to react certain time at a certain temperature, obtain pale yellow powder shape solid, concentrate solution of volatilizing, filtering,
Pulverulent solids are washed with suitable solvent, are then recrystallized by suitable solvent to get target product；It can also not have to anti-
Solvent is answered, directly two kinds of raw materials are mixed by the ratio between certain amount of substance, griding reaction under room temperature, obtained solid is with suitably
Solvent recrystallizes, also available target product.
Method is fifth is that amine is raw material using demethyl Chinese blister beetle acid imide and two (2- bromoethyls), and steps are as follows:
After demethyl Chinese blister beetle acid imide and two (2- bromoethyl) amine are dissolved in suitable organic solvent, according to certain substance
The mixing of the ratio between amount, be stirred to react certain time at a certain temperature, obtain pale yellow powder shape solid, concentrate solution of volatilizing,
Filtering, pulverulent solids are washed with suitable solvent, are then recrystallized by suitable solvent, obtain target product；It can not also
With reaction dissolvent, directly two kinds of raw materials are mixed by the ratio between certain amount of substance, griding reaction under room temperature, obtained solid is closed
Suitable solvent recrystallizes, also available target product.
Method four and method five are one-step reaction, their difference is reactant difference, but the molar ratio of reactant
Between 4:1 and 1:2.
Organic solvent (including reaction, washing, recrystallization solvent) in above five kinds of methods is selected from: methanol, ethyl alcohol, second
Nitrile, methylene chloride, chloroform, tetrahydrofuran, ethyl acetate, toluene, acetone, N,N-dimethylformamide (DMF) etc.；It is anti-in solid phase
Solvent is not had in answering.
Preferably, the reaction temperature and recrystallization temperature are room temperature or heating, and reaction method is stirring or stands, and are tied again
Crystal method is to volatilize naturally under static condition.
Preferably, the reaction time and recrystallization time are selected from: -3 days 2 hours.
The beneficial effects of the present invention are: more complicated fluorescent material can be synthesized with fairly simple step and reactant
And pesticide original medicine.
3, ultraviolet and photoluminescent property.
10-5It is stronger to find that it has near 236nm for the ultraviolet spectra that this compound is tested in mol/L ethanol solution
Ultraviolet absorption peak (as shown in Fig. 3).
Also in 10-5In mol/L ethanol solution, swashed respectively with the ultraviolet light that wavelength is 350nm, 370nm and 380nm
Hair, tests the photoluminescent property of this compound, it is found that it has strong fluorescent emission near 430nm, with the ultraviolet excitation of 370nm
The fluorescence of generation is especially strong, and the visible bluish violet fluorescence of naked eyes, fluorescence spectrum is shown in attached drawing 4.
4, insecticidal test.
Insecticidal test is experimental subjects with diamondback moth larvae, is tested with 75% ethanol solution, using leaching worm immersion method
The compound is measured to the synthesis virulence of diamondback moth larvae；According to the minimum full cause for the diamondback moth larvae that preliminary experiment is predicted
Dead concentration and highest are survived concentration entirely, 5-7 gradient concentration are set within this range, by each concentration medicine of 3 instar larvae of diamondback moth immersion
It is placed on blotting paper after 5 seconds in liquid and sucks the upper extra medical fluid of polypide, be put into cylindricality bottle (diameter 3.5cm, the height for being covered with moisturizing filter paper
In 7.5cm)；And soak cabbage leaves (size about 2cm × 2cm) 2-3 seconds in medical fluid, extra medical fluid is sucked, cylindricality bottle is put into
It is middle edible for larva；10 larvas per treatment, each concentration gradient repeat three times, using clear water processing as control；It will everywhere
Reason is put into weather incubator, controlled at 25 DEG C or so, relative humidity 75%.Photoperiod 14/10 (L/D)；After 24 hours
It checks dead larvae situation, virulence regression equation and lethal concentration of 50 LC50 is found out according to statistical result；Test result shows this
Compound is about 97mg/L to the LC50 value of diamondback moth larvae.
5, inhibit fungi experiment.
Active testing has been carried out to two kinds of phytopathogens (Pyricularia oryzae and tomato wilt) using fungus block method, has been trained
Supporting base is potato agar culture medium (PDA): peeled potatoes 200g, sucrose 15g, agar 17g, distilled water 1000ml；Mycelia
Fungus block is made in the sterilizing clamp dog device for being 0.8cm with diameter after length is good, then by fungus block sterilizing tweezers clamping, is put into containing 100mg/
The culture dish center of L compound solution (solvent is 25% ethanol solution), one piece of every ware, three one group of wares are placed in 27 DEG C of cultures
72h measures bacterial plaque diameter, and compares with blank assay, finds out mycelial growth inhibition rate with following formula:
Inhibiting rate=(control group average colony diameter-processing group average colony diameter) ÷ control group average colony diameter ×
100%
Test result shows that the compound is respectively 88% He to the inhibiting rate of Pyricularia oryzae and tomato wilt
86%.
6, specific embodiment
Content in order to better understand the present invention further illustrates technology of the invention below by five specific embodiments
Scheme.
Embodiment 1.
It weighs 3.32g unsaturation cantharidin (0.02mol) to be dissolved in 50mL toluene, be vigorously stirred, 1.03g is added
(0.01mol) diethylenetriamine has viscous light yellow solid precipitation after stirring 4h, solution is filtered, sticky solid dichloromethane
After alkane rinses, it is dissolved in ethanol solution, faint yellow granular solids are precipitated after 3d；Recrystallized again with methanol once can obtain it is colourless rodlike
Crystal, referred to as crystal A, ingredient 2,2'- (3- aza-pentane -1,5- diyl) two (3a, 4,7,7a- tetrahydro -4,7- rings
Oxygen -1,3- xylylenimine -1,3- diketone)；Crystal A0.50g is weighed, 40mL methanol is added, ultrasonic vibration 10min is added
0.05g palladium-carbon catalyst is passed through hydrogen, and 40 DEG C of reaction 8h, after reaction, filtering stands volatilization, after three days, analyses in solution
White powder little crystal grain out, as target product.
Embodiment 2.
0.33g unsaturation demethyl Chinese blister beetle acid imide is dissolved in 30ml acetone, is added two with the mass ratio of the material example 2:1
(2- bromoethyl) amine 0.23g, stirring at normal temperature for 24 hours, obtain light brown suspension, evaporate into residue about 10ml to solvent, filter, and use
Methylene chloride washing precipitating, then uses recrystallizing methanol, can obtain colourless rhabdolith, referred to as crystal A, ingredient 2,2'-
(3- aza-pentane -1,5- diyl) two (3a, 4,7,7a- tetrahydro -4,7- epoxy -1,3- xylylenimine -1,3- diketone)；It weighs
40mL methanol is added in crystal A0.50g, and 0.05g palladium-carbon catalyst is added in ultrasonic vibration 10min, is passed through hydrogen, 40 DEG C of reactions
8h, after reaction, filtering stand volatilization, and white powder crystal, as target product are precipitated after three days, in solution.
Embodiment 3.
0.26g 1,1'- (2,2'- azepine dialkyl group two (ethane -2,1- diyl)) two (1H- pyrrole-2,5-diones) are molten
0.14g furans is added in 50ml toluene, with the mass ratio of the material example 1:2 in solution, is heated to reflux after 10h concentrate solution to 20ml, mistake
Filter, washs precipitating with methylene chloride, then uses recrystallizing methanol, can obtain colourless rhabdolith, referred to as crystal A, ingredient is
(3a, 4,7,7a- tetrahydro -4,7- epoxy -1,3- the xylylenimine -1,3- two of 2,2'- (3- aza-pentane -1,5- diyl) two
Ketone)；It weighing crystal A0.50g, 40mL methanol is added, 0.05g palladium-carbon catalyst is added in ultrasonic vibration 10min, it is passed through hydrogen, 40
DEG C reaction 8h, after reaction, filtering stands volatilization, and after three days, white powder crystal, as target product are precipitated in solution.
Embodiment 4.
3.36g cantharidin is weighed, is put into mortar, 1.03g diethylenetriamine is added, grinds 4h under room temperature, obtains
The dissolution of 100ml methanol is added in paste, and filtering stands volatilization, after three days, white powder little crystal grain is precipitated in solution, as
Target product.
Embodiment 5.
3.34g demethyl Chinese blister beetle acid imide is weighed, is put into mortar, 2.31g bis- (2- bromoethyl) amine is added, is ground under room temperature
4h is ground, paste is obtained, the dissolution of 100ml methanol is added, filtering stands volatilization, and after three days, the small crystalline substance of white powder is precipitated in solution
Grain, as target product.
7, Detailed description of the invention
Attached drawing 1 is target compound1HNMR spectrogram.
Attached drawing 2 is target compound13CNMR spectrogram.
Attached drawing 3 is the UV-visible spectrum of target compound.
Attached drawing 4 is the fluorescence spectra of target compound.
Claims (3)
1. a kind of Chinese blister beetle acid imide dimer compound of diethylenetriamine chain link, the powdered crystal grain of white in appearance, fusing point
158.1-158.7 DEG C, molecular formula C20H25N3O6, structure is as follows:
2. the preparation method of Chinese blister beetle acid imide dimer compound as described in the appended claim 1, it is characterised in that: reacted with two kinds
Object is raw material, in methanol, ethyl alcohol, acetonitrile, methylene chloride, chloroform, tetrahydrofuran, ethyl acetate, toluene, acetone or N, N- diformazan
One-step or two-step reaction occurs in base formamide organic solvent, solvent can also not had to and directly complete reaction by two kinds of raw materials；
Steps are as follows for two-step reaction:
1) it after raw material 1 and raw material 2 being dissolved in above-mentioned organic solvent respectively, is mixed according to the ratio between 4:1 to the amount of 1:2 substance, normal
Temperature is heated to reflux under state and is stirred to react -3 days 2 hours, obtains colourless rhabdolith, is intermediate product, which can not also
With organic solvent, two kinds of direct mixed grindings of raw material react to obtain intermediate product；
2) it takes the intermediate product to be dissolved in above-mentioned organic solvent, appropriate palladium-carbon catalyst is added, is passed through hydrogen, in room temperature or heat back
It is stirred to react -3 days 2 hours, filters under stream mode, stand volatilization, pale yellow powder shape crystal grain, which is precipitated, after three days, in solution is
For target product；
Raw material 1 and raw material 2 can be selected from: unsaturated cantharidin and diethylenetriamine, or unsaturated demethyl Chinese blister beetle acyl
Imines and two (2- bromoethyl) amine or furans and 1,1'- (2,2'- azepine dialkyl group two (ethane -2,1- diyl)) two (1H- pyrroles
Cough up -2,5- diketone)；
Steps are as follows for single step reaction:
After raw material 1 and raw material 2 are dissolved in above-mentioned organic solvent respectively, mixed according to the ratio between 4:1 to the amount of 1:2 substance, in room temperature
Or be heated to reflux under state and be stirred to react -3 days 2 hours, white powdery solids are obtained, concentrate solution of volatilizing, filtering, powder
Shape solid is washed with above-mentioned solvent, is then recrystallized by above-mentioned solvent to get target product；It can also not have to reaction dissolvent,
Directly two kinds of raw materials are mixed by the ratio between 4:1 to the amount of 1:2 substance, griding reaction -3 days 2 hours under room temperature, obtained solid is used
Above-mentioned solvent recrystallizes, also available target product；
Raw material 1 and raw material 2 can be selected from cantharidins and diethylenetriamine or demethyl Chinese blister beetle acid imide and two (2- bromines
Ethyl) amine.
3. compound as described in claim 1 and its acceptable salt is preparing the application in pesticide, feature in Pesticide Science
It is, the pesticide is for preventing and treating diamondback moth larvae or Pyricularia oryzae or tomato wilt.
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| CN105601650A (en) * | 2016-03-18 | 2016-05-25 | 齐鲁工业大学 | Structure, preparation method and use of diethylenetriamine-based cantharidimide dimer derivative |
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| Norcantharimides, synthesis and anticancer activity: Synthesis of new norcantharidin analogues and their anticancer evaluation;Timothy A. Hill，等;《Bioorg. Med. Chem.》;20070620;第15卷;6126-6134页 |
| 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;228-240页 |
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