CN103497194B - A kind of many nitrogen bicyclic compound, preparation method and applications - Google Patents
A kind of many nitrogen bicyclic compound, preparation method and applications Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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Abstract
The invention belongs to pesticide field, it is provided that a kind of many nitrogen bicyclic compound, preparation method and applications, the molecular structural formula of this compound is as follows:
Description
Technical field
The invention belongs to pesticide field, relate to a kind of bactericide, be specifically related to a kind of Fused bicyclic conjunction of many nitrogen
Thing, preparation method and applications.
Background technology
The development of agricultural chemicals, develops towards efficient, safety, economy, non-harmful direction, some high toxicities,
High residue, agricultural chemicals to severe environmental pollution are eliminated in succession, and environmentally friendly, ultra high efficiency, Gao Xuan
The pesticide new variety of selecting property is favored by people.The outstanding feature of world pesticide exploitation at present is strong
While heightening activity, more focus on security, it is ensured that the safety of non-target organism, the mankind and environment, and
Having the trend that safety first, activity are taken second place, the exploitation of sterilization is the most all the more so.China's imitating from agricultural chemicals
System, progressively goes on the initiative of novel pesticide, but the initiative work of China's agricultural chemicals is only the starting stage.From one
A little compounds set out, and carry out structural change, thus develop chemical constitution and be different from the new product of former compound
Kind, reach improve activity and expand range.
The chloride compounds such as trichlorine isonitrile urea acid have been applied in agricultural, but due to this kind of chemical combination
Thing is the most unstable, and sustained release performance is poor, the root, stem and leaf of the crop that causes easily burning, and makes plant growth be limited
System.
Summary of the invention
The shortcomings and deficiencies existed for prior art, it is an object of the invention to provide a kind of drug effect prominent,
Many nitrogen bicyclic compound bactericide bactericide that activity is high and slow release is good.
In order to realize above-mentioned technical assignment, the present invention adopts the following technical scheme that and is achieved:
A kind of many nitrogen bicyclic compound, it is characterised in that the molecular structural formula of this compound is as follows:
In formula, R is O, S or NH, and X is Cl or Br.
The molecular structural formula of preferred many nitrogen bicyclic compound bactericide is as follows:
In formula, R is O, S or NH.
The preparation method of above-claimed cpd, the method specifically follows the steps below:
Step one, according to reaction equation (I) select reaction raw materials glyoxal, select reaction raw materials guanidine carbonate,
Urea or thiocarbamide, add water in there-necked flask, add guanidine carbonate, urea or thiocarbamide, dissolves mixed
It is warmed up to 50 DEG C after closing uniformly, adds glyoxal, be continuously heating to 90 DEG C, use hydrochloric acid regulation system
PH value is in the range of 1～2, and after isothermal reaction 8h, washing and filtering obtains intermediate product；
Step 2, intermediate product step one prepared and water add in reaction bulb, according to reaction equation (II)
React, maintain the temperature at less than 10 DEG C, adjust with NaOH while logical chlorine or addition bromine
Joint pH value so that in the range of the pH value in system is maintained at 2～5, after reaction 6h, uses hydroxide
Sodium regulation pH is in the range of 6～7, and washing and filtering obtains product.
Above-mentioned many nitrogen bicyclic compound is for the application as bactericide.
Present invention advantage compared with prior art:
(1) bactericidal activity of the compound of the present invention is significantly higher than other same series bactericidal agents existing, such as three
Chlorine isourea acid and virus must gram.Experiment bacterium, under 500ppm concentration, is had by the bactericide of the present invention
The inhibiting rate of 100%.
(2) material stability of the compound of the present invention is good, tests, resolution ratio 72% in 5 days in water.
(3) compound of the present invention is in ambient-temp-stable cenotype to preferably, and heat storage resolution ratio is less than 15%.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of LDQ-1.
Fig. 2 is the infrared spectrogram of LDQ-2.
Fig. 3 is the infrared spectrogram of LDQ-3.
Below in conjunction with drawings and Examples, technical scheme is described further.
Detailed description of the invention
Following embodiment provides a kind of many nitrogen bicyclic compound, the following institute of molecular structural formula of this compound
Show:
In formula, R is O, S or NH, and X is Cl or Br.
In the structure of above-mentioned many nitrogen bicyclic compound, being O, S or NH at R, compound forms one
Individual big rock-steady structure, it is possible to the most stable, improves the stability of this class formation, prays the work of sustained release
With, this compounds is in slow decomposable process simultaneously, discharges substantial amounts of nitrogen, and the production for plant carries
Having supplied abundant nitrogen source, beneficially crop opposing disease, promotes growth.
It should be noted that X only provides embodiment using Cl as representative in the following embodiments, Cl and
Br is congeners, can mutually replace in this compound, and effect is identical.
Preferred many nitrogen bicyclic compound, the molecular structural formula of this many nitrogen bicyclic compound is as follows:
In formula, R is O, S or NH.
The method preparing above-claimed cpd, the method specifically follows the steps below:
Step one, according to reaction equation (I) select reaction raw materials glyoxal, select reaction raw materials guanidine carbonate,
Urea or thiocarbamide, add water in there-necked flask, add guanidine carbonate, urea or thiocarbamide, dissolves mixed
It is warmed up to 50 DEG C after closing uniformly, adds glyoxal, be continuously heating to 90 DEG C, use hydrochloric acid regulation system
PH value is in the range of 1～2, and after isothermal reaction 8h, washing and filtering obtains intermediate product；
Step 2, intermediate product step one prepared and water add in reaction bulb, according to reaction equation (II)
React, maintain the temperature at less than 10 DEG C, adjust with NaOH while logical chlorine or addition bromine
Joint pH value so that in the range of the pH value in system is maintained at 2～5, after reaction 6h, uses hydroxide
Sodium regulation pH is in the range of 6～7, and washing and filtering obtains product.
Above-claimed cpd, for the application as bactericide, is mainly used in effecting a radical cure bacterial propagule, bacterium bud
The disease of agricultural plants that spore and various viral pathogen cause, the compound that the present embodiment is given simultaneously is one
Planting preferable environmental type antisepsis antistaling agent, vegetables, melon and fruit make after the ripe collecting period uses or gathers in the crops
The compound be given with the present embodiment, can play good corrosion-resistanting fresh-keeping effect, has and well kills respectively
Plant bacterium, algae, fungi and the effect of virus.
Mol ratio relation between glyoxal and guanidine carbonate, urea or thiocarbamide control at 1:(2～
2.50) in the range of so that guanidine carbonate, urea or thiocarbamide are the most excessive, chlorine or bromine are the most excessive, profit
Carry out in reaction.
The specific embodiment of the present invention given below, it should be noted that and the invention is not limited in following tool
Body embodiment, all equivalents done on the basis of technical scheme each fall within the protection model of the present invention
Enclose.
Embodiment 1:
The present embodiment provides the preparation method of a kind of many nitrogen bicyclic compound, specifically includes following steps:
Step one, in 500ml there-necked flask, adds 100ml water and 90g guanidine carbonate, mixes
And it is warmed up to 50 DEG C, add the glyoxal 60ml that mass fraction is 40%, be continuously heating to 90 DEG C,
By hydrochloric acid (mass fraction is 37.5%) regulation system pH value between 1～2, after isothermal reaction 8h,
With 50ml water washing and filtering twice, obtain diimide imidazolidine 35g；
Step 2,35g diimide imidazolidine step one prepared and 100ml water add in reaction bulb,
Logical chlorine below 10 DEG C, adjusts pH value with NaOH (mass fraction is 15%) so that body simultaneously
In the range of pH value in system is maintained at 2～5, after reaction 6h, with NaOH regulation pH 6～7
In the range of, washing with water and being filtrated to get product is 69g, and purity is 96% (HPLC), this product
Being designated as LDQ-1, its molecular structural formula is as follows:
Product structure is identified:
The infrared spectrogram of LDQ-1 as it is shown in figure 1, IR (KBr, cm-1): 3320 (N-H),
1702 (C=N), 1280～1192 (C-N), 607 (N-Cl).
1H NMR (DMSO, δ ppm): 5.12 (2H, s).
Elementary analysis: C4H4N6Cl4, theoretical value (%): C17.27, H0.01439, N30.22；Real
Measured value (%): C17.45, H0.00, N30.70.
Confirm that the material that the present embodiment prepares is that in the present embodiment, chemical formula represents according to above-mentioned appraising datum
Material.
Embodiment 2:
The present embodiment provides the preparation method of a kind of many nitrogen bicyclic compound, specifically includes following steps:
Step one, in 500ml there-necked flask, adds 100ml water and 60g urea, mixes also
It is warmed up to 50 DEG C, adds the glyoxal 60ml that mass concentration is 40%, be continuously heating to 90 DEG C, use
Hydrochloric acid (mass fraction is 37.5%) regulation system pH value is between 1～2, after isothermal reaction 8h,
With 50ml water washing and filtering twice, obtain double imidazolidinone 35g；
Step 2, the double imidazolidinone of 35g step one prepared and 100ml water add in reaction bulb,
Less than 10 DEG C logical chlorine, adjust pH value with NaOH (mass fraction is 15%) so that system simultaneously
In pH value be maintained at 2～5 in the range of, reaction 6h after, with NaOH regulation pH at 6～7 models
In enclosing, washing with water and being filtrated to get product is 25g, and purity is 95% (HPLC), and this product is designated as
LDQ-2, its molecular structural formula is as follows:
Product structure is identified:
The infrared spectrogram of LDQ-2 as in figure 2 it is shown, IR (KBr, cm-1): 1775 (C=O),
1373,1170 (C-N), 776 (N-Cl).
1H NMR (DMSO, δ ppm): 6.87 (2H, s).
Elementary analysis: C4H2N4O2Cl4, theoretical value (%): C17.14, H0.0071, N20.00 are real
Measured value (%): C17.8, H0.00, N20.71.
Confirm that the material that the present embodiment prepares is that in the present embodiment, chemical formula represents according to above-mentioned appraising datum
Material.
Embodiment 3:
The present embodiment provides the preparation method of a kind of many nitrogen bicyclic compound, specifically includes following steps:
Step one, in 500ml there-necked flask, adds 100ml water and 76g thiocarbamide, mixes also
It is warmed up to 50 DEG C, adds the glyoxal 60ml of 40%, be continuously heating to 90 DEG C, by hydrochloric acid (quality
Mark is 37.5%) regulation system pH value between 1～2, after isothermal reaction 8h, use 50ml water
Washing and filtering twice, obtains double imidazole thione 35g；
Step 2, the double imidazole thione of 35g step one prepared and 100ml water add in reaction bulb,
Less than 10 DEG C logical chlorine, adjust pH value with NaOH (mass fraction is 15%) so that system simultaneously
In pH value be maintained at 2～5 in the range of, reaction 6h after, with NaOH regulation pH at 6～7 models
In enclosing, washing with water and being filtrated to get product is 32g, and purity is 93% (HPLC), and this product is designated as
LDQ-3, its molecular structural formula is as follows:
Product structure is identified:
The infrared spectrogram of LDQ-3 as it is shown on figure 3, IR (KBr, cm-1): 1689 (C=S),
1258,1133 ((C-N), 764,643 (N-Cl).
1H NMR (DMSO, δ ppm): 4.32 (2H, s).
Elementary analysis: C4H2N4S2Cl4, theoretical value (%): C15.38, H0.0064, N17.95 are real
Measured value (%): C15.70, H0.00, N18.43.
Confirm that the material that the present embodiment prepares is that in the present embodiment, chemical formula represents according to above-mentioned appraising datum
Material.
Application effect example:
It is 96% by the former medicine of cyazofamid that reagent agent purity is 94.5% with compareing medicament purity
LDQ-1, purity be 95% LDQ-2 and the former medicine of LDQ-3 that purity is 93% weigh respectively 0.053g,
0.052g, 0.052 and 0.053g, be then respectively adding four sterilizing triangles having added 2mL acetone in advance
In Ping, and adding 0.01g Tween 80 #, fully vibration makes it dissolve, and is subsequently adding sterilized water to 100
ML, makes each 100mL of experiment mother liquor that concentration is 500 μ g/g standby.
On the basis of preliminary experiment, each experiment mother liquor is configured to respectively the solution of 3 concentration gradients,
3 concentration gradients are followed successively by 500 μ g/g, 250 μ g/g, 125 μ g/g, during preparation band medicine culture medium,
Concentration dilutes 10 times again, is followed successively by 50 μ g/g, 25 μ g/g, 12.5 μ g/g.In aseptic technique
Under, the sterilising medium 18mL melted in advance is added in aseptic conical flask, from low concentration to highly concentrated
Degree draws liquid 2mL successively, is separately added in above-mentioned aseptic conical flask, fully shakes up.Immediately after
Pour in the culture dish of 12 a diameter of 9cm, make the pastille culture medium of respective concentration, separately set not pastille
The culture medium without medicine of liquid makees blank, often processes and is repeated 4 times.
By the pathogen of cultured Phytophthora infestans germ, aseptically beating with a diameter of 5mm
Hole device, cuts bacterium cake from colony edge, with transfer needle by pure culture biscuits involvng inoculation in pastille flat board central authorities, mycelia face
By culture medium, cover ware lid, put cultivation 72h in 20 DEG C of insulating boxs.
Using kind of calliper colony diameter, unit is millimeter (mm).After cultivating 72h for examination bacterium colony, often
Individual bacterium colony uses right-angled intersection method vertical survey diameter each once, takes its mean value, its measurement result such as table
Shown in 1.
Table 1 medicament is to Phytophthora infestans germ Toxicity Determination result
As can be seen from Table 1, above-described embodiment many nitrogen bicyclic compound LDQ-1, LDQ-2 and
LDQ-3 is to having more significantly inhibitory activity, better than contrast agents to Phytophthora infestans germ.
The sterilization mechanism of chloride bactericide is that such material is decomposed into hypochlorous acid in water, and then hypochlorous acid divides
Solving and form nascent oxygen, the extremely strong oxidisability of nascent oxygen makes the materials such as the protein in thalline and virus become
Property, thus lethal sex pheromone.Secondly, hypochlorous acid, during sterilization, killing the virus, not only can be made
For cell membrane, virus coat, and because hypochlorous acid molecule is little, neutral, also can penetrate into bacterium (sick
Poison) internal, and the organic polymer generation oxidation reaction such as bacterium (viral) body protein, nucleic acid and enzyme,
Thus kill pathogenic microorganism.Meanwhile, the chlorion that hypochlorous acid produces can also significantly change bacterium and disease
Poison body osmotic pressure so that it is cell loss activity and dead.
Claims (1)
1. the preparation method of nitrogen bicyclic compound more than a kind, it is characterised in that the method is specifically according to following
Step is carried out:
Step one, selects reaction raw materials glyoxal according to reaction equation (I), selects reaction raw materials guanidine carbonate,
In there-necked flask, add water, add guanidine carbonate, dissolve and be warmed up to 50 DEG C after mixing, add second
Dialdehyde, is continuously heating to 90 DEG C, in the range of hydrochloric acid regulation system pH value to 1～2, and isothermal reaction 8h
After, washing and filtering obtains intermediate product,
Step 2, intermediate product step one prepared and water add in reaction bulb, according to reaction equation (II)
React, maintain the temperature at less than 10 DEG C, regulate with NaOH while logical chlorine or addition bromine
PH value so that in the range of the pH value in system is maintained at 2～5, after reaction 6h, adjusts with NaOH
Joint pH is in the range of 6～7, and washing and filtering obtains product,
Described product is many nitrogen bicyclic compound, and the molecular structural formula of this compound is as follows:
In formula, X is Cl or Br.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1141718A (en) * | 1995-07-31 | 1997-02-05 | 陕西省蚕桑研究所 | Qiangluan-compound disinfectant for silkworm |
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2013
- 2013-09-24 CN CN201310451799.1A patent/CN103497194B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1141718A (en) * | 1995-07-31 | 1997-02-05 | 陕西省蚕桑研究所 | Qiangluan-compound disinfectant for silkworm |
Non-Patent Citations (2)
| Title |
|---|
| 四溴甘脲对枯草杆菌黑色变种芽胞损伤作用的电镜观察;张凤云等;《生物学杂志》;20061231;第23卷(第6期);第43-44页 * |
| 溴氯甘脲系列消毒剂杀灭细菌牙胞的实验观察;赵进沛等;《现代预防医学》;20071231;第34卷(第1期);第120-121页 * |
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