CN101885707A - Triazine derivative and preparation method thereof as well as new application as insecticide - Google Patents
Triazine derivative and preparation method thereof as well as new application as insecticide Download PDFInfo
- Publication number
- CN101885707A CN101885707A CN200910084470XA CN200910084470A CN101885707A CN 101885707 A CN101885707 A CN 101885707A CN 200910084470X A CN200910084470X A CN 200910084470XA CN 200910084470 A CN200910084470 A CN 200910084470A CN 101885707 A CN101885707 A CN 101885707A
- Authority
- CN
- China
- Prior art keywords
- formula
- preferred
- triazine derivative
- reaction
- general structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a triazine derivative and a preparation method and an application thereof. The structural general formula of the triazine derivative is shown in formula I. The preparation method of the triazine derivative comprises the following two modes: (1) reacting cynuric chloride with secondary amine under the temperature of 1-150 DEG C for 0-100 hours to obtain the product; and (2) reacting cynuric chloride with secondary amine under the temperature of 0-150 DEG C for 0-100 hours to obtain the product, wherein R1, R2, R3, R4, R5 and R6 is H and C1-C6 alkyl group. The triazine derivative provided by the invention has simple synthetic method, has good insecticidal activity, has good elimination activity for red spiders under the dosage of 20mg/L, can be applied to preparing the pesticides, has the advantages of low toxicity and no harm to crops, is beneficial to environment and has wide application prospect in the pesticides field.
Description
Technical field
The present invention relates to a kind of triazine derivative and preparation method thereof and new purposes as sterilant.
Background technology
In recent years, again and again a new problem arose on agricultural insect pests control, the wildness of insects such as small cabbage moth, beet armyworm and trialeurodes vaporariorum for example, insect such as the snout moth's larva of rice and planthopper is to the serious resistance of medicament commonly used, add that riskiest pesticide is cut down and the enforcement of forbidding plan, very urgent to the development requires of sterilant new variety.Therefore, can be used to solve difficult pest control problem and be expected to enter the sterilant that riskiest pesticide substitutes ranks, beyond doubt the focus kind of industry common concern.Wherein, heterocyclic insecticides also will continue to play the part of crucial role.Through the continuous effort of people, successfully developed insecticide varieties such as nicotinoids, arylpyrazoles, pyrazol acid amide, aryl pyrrolines and oxadiazines class, wherein indenes worm prestige is as the widely used outstanding sterilant of being represented as of oxadiazines insecticides.With the triazine is present develop also less of sterilant of skeleton.
Summary of the invention
The invention provides a kind of triazine derivative and preparation method thereof and new purposes as sterilant.
Triazine derivative provided by the invention, its general structure is suc as formula shown in the I:
(formula I)
(formula II) (formula III)
In the above-mentioned formula I general structure, R
1, R
2, R
3, R
4, R
5, R
6All being selected from H and backbone c atoms number is C
1-C
6Alkyl.R
1, R
2, R
3, R
4, R
5, R
6Can be identical group, also can be different groups.R
1, R
2, R
3, R
4, R
5, R
6Can be in the following radicals any one: hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-pentyl, 2-methyl butyl, 3-methyl butyl, n-hexyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1-methyl amyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl.Wherein, R
1, R
2, R
3, R
4, R
5, R
6All preferred hydrogen, methyl, n-propyl, sec.-propyl, normal-butyl, 3-methyl-propyl.In the formula II general structure, R
1, R
2, R
3, R
4, R
5, R
6All being selected from H and backbone c atoms number is C
1-C
6Alkyl.In the formula III general structure, R
1, R
2, R
3, R
4, R
5, R
6All being selected from H and backbone c atoms number is C
1-C
6Alkyl.
In the formula I structure general formula provided by the invention, R
3Be methyl, R
4During for H, be compound shown in the formula V, in the formula V general structure, R
1, R
2All be selected from C
2-C
6Alkyl.
(formula V)
The method of the above-mentioned triazine derivative II of preparation provided by the invention comprises following two kinds of methods:
One, the secondary amine shown in Cynuric Chloride and the formula II general structure is reacted, obtain triazine derivative provided by the invention;
Two, the primary amine shown in Cynuric Chloride and the formula III general structure is reacted, obtain triazine derivative provided by the invention;
In formula II and the formula III general structure, R
1, R
2, R
3, R
4, R
5, R
6Can be identical group, also can be different groups, R
1, R
2, R
3, R
4, R
5, R
6Can be in the following group any one: hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-pentyl, 2-methyl butyl, 3-methyl butyl, n-hexyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1-methyl amyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl.
In above-mentioned two methods, the mol ratio of secondary amine shown in Cynuric Chloride and the formula II general structure or the primary amine shown in the formula III general structure is 1: 1-1: 20, and preferred 1: 3.Temperature of reaction is 0-150 ℃, preferred 80 ℃; Reaction times is 0-100 hour, preferred 24 hours.Reaction medium be in acetone, methylene dichloride, trichloromethane, ether, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), dioxane or the acetonitrile any one or arbitrarily several with arbitrary proportion blended mixture, preferred tetrahydrofuran (THF).Reaction system also adds alkali; Described alkali is yellow soda ash, salt of wormwood, sodium bicarbonate or sodium hydroxide, preferred yellow soda ash.The mol ratio of described alkali and described Cynuric Chloride is 10: 1-1: 2, and preferred 3: 1.
Compound shown in the formula V also can be prepared as follows:
1) under-20 ℃ of-10 ℃ of conditions, the reaction of cyanuric chloride and aqueous methylamine solution is finished, add alkali then and continue reaction after 60-180 minute, be warming up to 15-80 ℃, obtain intermediate formula V compound; Wherein, alkali is yellow soda ash, salt of wormwood, sodium bicarbonate or sodium hydroxide, preferred yellow soda ash;
2) be R with intermediate formula V compound and substituting group
1And R
2Diamines 30-150 ℃ of reaction, obtain triazine derivative;
Wherein, substituent R
1, R
2Be C
2-C
6Alkyl.R
1And R
2Can be identical group, also can be different groups.R
1, R
2Can be in the following radicals any one: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-pentyl, 2-methyl butyl, 3-methyl butyl, n-hexyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1-methyl amyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl.
In the step 1) of aforesaid method, the temperature of reaction of cyanuric chloride and aqueous methylamine solution is preferably 0 ℃ of ice bath, and the reaction times is 5-120 minute, and the mass percent concentration of aqueous methylamine solution is 15%-50%, and preferred 33%; The mol ratio of cyanuric chloride and aqueous methylamine solution is 2: 1-1: 5, and preferred 1: 2; The mol ratio of alkali and cyanuric chloride is 1: 1-1: 5, and preferred 1: 2; Solvent for use is selected from least a in acetone, methylene dichloride, trichloromethane, ether, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), dioxane and the acetonitrile, is preferably acetone; Step 2) solvent for use is selected from acetone, methylene dichloride, trichloromethane, ether, tetrahydrofuran (THF), N, and at least a in dinethylformamide, dioxane and the acetonitrile is preferably N, dinethylformamide.
Step 2) temperature of reaction is preferably 100 ℃, and the reaction times is 2h-36h, and intermediate formula V compound and substituting group are R
1And R
2The mol ratio of diamines be 2: 1-1: 5, preferred 1: 1.
With triazine derivative provided by the present invention is that the sterilant of activeconstituents also belongs to protection scope of the present invention.In actually operating,, can in above-mentioned triazine derivative sterilant, add various assistant agents as required for reaching better insecticidal effect.In addition, the application of triazine derivative provided by the present invention in the preparation sterilant also belongs to protection scope of the present invention.
Triazine derivative provided by the invention, simple synthetic method, product has excellent insecticidal activity to paddy rice brown paddy plant hopper, mythimna separata, red spider, aphis craccivora etc., under 20mg/L dosage, red spider had and well kill activity, can be used for preparing agricultural chemical insecticide, low toxicity does not injure crop, environmental friendliness has broad application prospects in the agricultural chemical insecticide field.
Embodiment
The present invention will be further described below in conjunction with embodiment, but the present invention is not limited to following examples.
The triazine derivative of embodiment 1, preparation formula I general structure (1)
2.03g (11mmol) Cynuric Chloride compound is dissolved in the 50ml acetone, with 10.1g (100mmol) N, the N-di-n-propyl amine is dissolved in the 50ml acetone, and the acetone soln of Cynuric Chloride is placed the 500ml three-necked bottle, under 0 ℃ to wherein dripping N, the acetone soln of N-di-n-propyl amine, dropwise the back and refluxed 8 hours, reaction is poured in the water, uses extracted with diethyl ether, wash with water (5 * 100ml), dried over sodium sulfate.Obtain the triazine derivative shown in the formula I (1), be white solid 1.25g, productive rate 30%.
Ultimate analysis: molecular formula C
21H
42N
6, molecular weight 378
Theoretical value: C 66.62 H 11.18 N 22.20; Measured value: C 66.68 H 11.27 N 22.21
Nucleus magnetic resonance: 3.40 (t, J=7.2Hz, 12H), 1.58 (m, J=7.2Hz, 12H), 0.88 (t, J=7.2Hz, 18H); 165.08,49.13,21.56,11.55.
Mass spectrum: [M+H]
+379.
Show that this compound structure is correct.
The triazine derivative of embodiment 2, preparation formula I general structure (2)
With 4.29g (33mmol) N, N-di-n-butyl amine and 9.54g yellow soda ash (30mmol) are dissolved in 70ml water and join in the 500ml three-necked bottle, 1.845g (10mmol) Cynuric Chloride is dissolved in tetrahydrofuran (THF), in three-necked bottle, drips the tetrahydrofuran solution of Cynuric Chloride, refluxed 24 hours.The reactant extracted with diethyl ether (3 * 60ml), dried over sodium sulfate.Obtain colourless liquid 3.27g, productive rate is 70%, is the triazine derivative (2) of formula I general structure.
Ultimate analysis: molecular formula C
27H
54N
6, molecular weight 462
Theoretical value: C 70.08 H 11.76 N 18.16 measured values: C 70.93 H 11.77 N 17.47
Nucleus magnetic resonance: 3.44 (t, J=7.6Hz, 12H), 1.55 (m, J=7.4Hz, 12H), 1.29 (m, J=7.2Hz, 12H), 0.90 (t, J=7.8Hz, 18H); 165.02,46.89,30.56,20.45,14.06.
Mass spectrum: [M+H]
+463.
Show that this compound structure is correct.
The triazine derivative of embodiment 3, preparation formula I general structure (3)
With 4.29g (33mmol) N, N-two (2-methyl) propyl group amine and 3.18g yellow soda ash (10mmol) are dissolved in the 70ml water and join in the 250ml three-necked bottle, the 1.845g Cynuric Chloride is dissolved in the 15ml tetrahydrofuran (THF), in three-necked bottle, drip the tetrahydrofuran solution of Cynuric Chloride, refluxed 30 hours.The reactant suction filtration, use ethanol: the mixed solvent of water=1: 1 washs, and column chromatography obtains white solid 3.36g, for being the triazine derivative (3) of formula I general structure
Ultimate analysis: molecular formula C
27H
54N
6Molecular weight 462
Theoretical value: C 70.08 H 11.76 N 18.16 measured values: C 70.45 H 11.95 N 18.28
Nucleus magnetic resonance: 3.29 (d, J=7.2Hz, 12H), 2.15 (m, J=6.9Hz, 6H), 0.90 (d, J=6.9Hz, 36H); 165.41,55.77,27.40,20.55.
Mass spectrum: [M+H]
+463.
Show that this compound structure is correct.
The triazine derivative of embodiment 4, preparation formula I general structure (4)
Be dissolved in 3.90g (66mmol) Tri N-Propyl Amine and 8.28g (60mmol) salt of wormwood in the 100ml water and place a 250ml two-mouth bottle, 1.84g (10mmol) Cynuric Chloride is dissolved among the 20ml DMF, drip the DMF solution of Cynuric Chloride in two-mouth bottle, 100 ℃ were stirred 40 hours down.(3 * 80ml), organic phase is washed with saturated sodium-chloride water solution, and anhydrous sodium sulfate drying is spin-dried for solvent, column chromatography for separation with extracted with diethyl ether.Obtain white solid 1.02g, productive rate is 40.5%.Triazine derivative (4) for the II general structure.
Ultimate analysis: molecular formula C
12H
24N
6, molecular weight 252
Theoretical value: C 57.11 H 9.59 N 33.30; Measured value: C 57.21 H 9.61 N 33.06
Nucleus magnetic resonance: 3.29 (d, J=7.2Hz, 12H), 2.15 (m, J=6.9Hz, 6H), 0.90 (d, J=6.9Hz, 36H); 165.41,55.77,27.40,20.55.
Mass spectrum: [M+H]
+253.
Show that this compound structure is correct.
The triazine derivative of embodiment 5, preparation formula I general structure (5)
7.2g (99mmol) n-Butyl Amine 99 and 12.42g (90mmol) salt of wormwood are dissolved in 100ml water and pour in the 500ml there-necked flask, 1.845g (10mmol) Cynuric Chloride is dissolved in methyl alcohol, and this methanol solution splashed in the there-necked flask, system is in 40 ℃ of reactions 80 hours down.(3 * 80ml), anhydrous sodium sulfate drying is spin-dried for solvent to reaction product, column chromatography for separation with extracted with diethyl ether.Obtain white solid 1.29g, productive rate is 43.9%, is the triazine derivative (5) of formula I general structure.
Ultimate analysis: molecular formula C
15H
30N
6, molecular weight 294
Theoretical value: C 61.19 H 10.27 N 28.54; Measured value: C 61.19 H 10.26 N 28.24
Nucleus magnetic resonance: 4.75 (br, 3H), 3.34 (m, 6H), 1.53 (m, J=7.2Hz, 6H), 1.39 (m, J=7.2Hz, 6H), 0.93 (t, J=7.2Hz, 9H); 166.30,40.34,32.00,20.03,13.72.
Mass spectrum: [M+H]
+295.
Show that this compound structure is correct.
The triazine derivative of embodiment 6, preparation formula I general structure (6)
Be dissolved in 0.8g (10mmol) 2-methyl propylamine and 1.38g (10mmol) salt of wormwood in the 100ml water and place a 250ml two-mouth bottle, 1.84g (10mmol) Cynuric Chloride is dissolved in the 20ml tetrahydrofuran (THF), drip the tetrahydrofuran solution of Cynuric Chloride in two-mouth bottle, 40 ℃ were stirred 72 hours down.The reactant cooling to wherein adding 60ml water, adds the aqueous solution that contains 1.2g sodium hydroxide, regulates pH=9, and (3 * 80ml), organic phase is washed with saturated sodium-chloride water solution, and anhydrous sodium sulfate drying is spin-dried for solvent, column chromatography for separation with extracted with diethyl ether.Get white solid 0.67g, productive rate is 23%, is the triazine derivative (6) of formula I general structure
Ultimate analysis: molecular formula C
15H
30N
6, molecular weight 294
Theoretical value: C61.19 H 10.27 N 28.54 measured values: C 60.67 H 10.20 N 28.03
Nucleus magnetic resonance: 4.85 (br, 3H), 3.18 (m, 6H), 1.82 (m, J=6.9Hz, 3H), 0.93 (d, J=6.9Hz, 18H); 166.45,48.24,28.65,20.17.
Mass spectrum: [M+H]
+295.
Show that this compound structure is correct.
The triazine derivative of embodiment 7, preparation formula I general structure (7)
Be dissolved in 1.18g (40mmol) Tri N-Propyl Amine and 4.24g (40mmol) yellow soda ash in the 70ml water and join in the 250ml three-necked bottle, with 1.735g (10mmol) 6-chloro-2,4-dimethylamino-1,3, the 5-triazine is dissolved in the 15ml tetrahydrofuran (THF), drips 6-chloro-2,4-dimethylamino-1 in three-necked bottle, 3, the tetrahydrofuran solution of 5-triazine, 85 ℃ were stirred 25 hours down, reactant extracted with diethyl ether (3 * 80ml), anhydrous sodium sulfate drying, column chromatography for separation.Obtain yellow thick material 0.70g, productive rate is 35.7%, the triazine derivative of formula I general structure (7).
Ultimate analysis: molecular formula C
8H
16N
6Molecular weight 196
Theoretical value: C 48.96 H 8.22 N 42.82 measured values: C 47.9 H 8.14 N 43.27
Nucleus magnetic resonance: 5.51 (br, 2H), 5.33 (br, 1H), 3.31 (m, 2H), 2.89 (d, J=4.5Hz, 6H), 1.55 (m, J=7.2Hz, 2H), 0.93 (t, J=7.2Hz, 3H); 166.69,166.14,42.39,27.38,23.00,11.38.
Mass spectrum: [M+H]
+197.
Show that this compound structure is correct.
The triazine derivative of embodiment 8, preparation formula I general structure (8)
Be dissolved in 5.84g (60mmol) n-Butyl Amine 99 and 6.36g (60mmol) yellow soda ash in the 100ml water and join in the 500ml three-necked bottle, with 1.735g (10mmol) 6-chloro-2,4-dimethylamino-1,3, the 5-triazine is dissolved in the 15ml tetrahydrofuran (THF), in three-necked bottle, drip 6-chloro-2,4-dimethylamino-1,3, the tetrahydrofuran solution of 5-triazine, 80 ℃ were stirred 10 hours down, reactant extracted with diethyl ether (3 * 80ml), organic phase is washed with saturated sodium-chloride water solution, anhydrous sodium sulfate drying, column chromatography for separation.Obtain yellow thick material 1.00g, productive rate is 47.6%, the triazine derivative of formula I general structure (8).
Ultimate analysis: molecular formula C
9H
18N
6Molecular weight 210
Theoretical value: C 51.41 H 8.63 N 39.97 measured values: C 51.42 H 8.79 N 39.12
Nucleus magnetic resonance: 4.84 (br, 3H), 3.35 (m, 2H), 2.91 (d, J=4.8Hz, 6H), 1.53 (m, J=7.2Hz, 2H), 1.34 (m, J=7.2Hz, 2H), 0.93 (t, J=7.2Hz, 3H); 166.80,166.24,40.32,31.97,27.45,20.01,13.71.
Mass spectrum: [M+H]
+211.
Show that this compound structure is correct.
The triazine derivative of embodiment 9, preparation formula I general structure (9)
Be dissolved in 1.46g (20mmol) 2-methyl propylamine and 2.12g (20mmol) yellow soda ash in the 50ml water and join in the 100ml three-necked bottle, with 1.735g (10mmol) 6-chloro-2,4-dimethylamino-1,3, the 5-triazine is dissolved in the 15ml tetrahydrofuran (THF), in three-necked bottle, drip 6-chloro-2,4-dimethylamino-1,3, the tetrahydrofuran solution of 5-triazine, 80 ℃ were stirred 50 hours down, reactant extracted with diethyl ether (3 * 80ml), organic phase is washed with saturated sodium-chloride water solution, anhydrous sodium sulfate drying, column chromatography for separation.Obtain yellow thick material 0.94g, productive rate is 44.8%, the triazine derivative of formula I general structure (9).
Ultimate analysis: molecular formula C
9H
18N
6Molecular weight 210
Theoretical value: C 51.41 H 8.63 N 39.97 measured values: C 51.29 H 8.92 N 39.28
Nucleus magnetic resonance: 4.85 (br, 3H), 3.18 (m, 2H), 2.91 (d, J=4.8Hz, 6H), 1.81 (m, J=6.9Hz, 1H), 0.94 (d, J=6.9Hz, 6H); 166.83,166.42,48.20,28.65,27.46,20.17.
Mass spectrum: [M+H]
+211.
Show that this compound structure is correct.
The triazine derivative of embodiment 10, preparation formula I general structure (10)
In two mouthfuls of bottles of a 500ml, add the 60ml mixture of ice and water, ice bath stirs, the Cynuric Chloride of 18.45g (100mmol) is dissolved in acetone makes solution, this solution is poured in two mouthfuls of bottles, splash into the dimethylamine agueous solution of 27g (200mmol) 33% with constant pressure funnel, remove ice bath, splash into the aqueous solution 40ml that is dissolved with 10.6g (100mmol) yellow soda ash, system is heated to 50 ℃, reacts 10 minutes.The reaction product extracted with diethyl ether, dried over sodium sulfate is spin-dried for solvent.Obtain the 17.5g white solid, productive rate is 86%, is 6-chloro-2,4-two (N, N-dimethyl) amino-1,3,5-triazines.With 2.02g (20mmol) N, N-di-n-propyl amine and 0.69g (5mmol) salt of wormwood is dissolved in the 50ml water and joins in the 100ml three-necked bottle, with 2.015g (10mmol) 6-chloro-2,4-two (N, the N-dimethyl) amino-1,3,5-triazines is dissolved in the tetrahydrofuran (THF), and this solution splashed in the three-necked bottle reaction 24 hours down of 70 ℃ of systems.Reaction product extracted with diethyl ether (60ml * 3), the alkali alumina column chromatography.Obtain colourless liquid 0.76g, productive rate 28.8% is the triazine derivative (10) of formula I general structure.
Ultimate analysis: molecular formula C
13H
26N
6Molecular weight 266
Theoretical value: C 58.61 H 9.84 N 31.55 measured values: C 58.52 H 9.88 N 31.31
Nucleus magnetic resonance: 3.45 (t, J=7.2Hz, 4H), 3.08 (s, 12H), 1.58 (m, 4H), 0.88 (t, J=7.5Hz, 6H); 166.01,165.28,48.71,35.74,21.35,11.53.
Mass spectrum: [M+H]
+267.
Show that this compound structure is correct.
The triazine derivative of embodiment 11, preparation formula I general structure (11)
With 12.9g (100mmol) N, N-di-n-butyl amine and 0.69g (5mmol) salt of wormwood is dissolved in the 100ml water and joins in the 500ml three-necked bottle, with 2.015g (10mmol) 6-chloro-2,4-two (N, the N-dimethyl) amino-1,3,5-triazines is dissolved in the tetrahydrofuran (THF), and this solution splashed in the three-necked bottle reaction 36 hours down of 60 ℃ of systems.Reaction product extracted with diethyl ether (60ml * 3), the alkali alumina column chromatography.Obtain colourless liquid 0.56g, productive rate 19.1% is the triazine derivative (10) of formula I general structure.
Ultimate analysis: molecular formula C
15H
30N
6Molecular weight 294
Theoretical value: C 61.19 H 10.27 N 28.54 measured values: C 61.03 H 10.36 N 28.54
Nucleus magnetic resonance: 3.49 (t, J=7.5Hz, 4H), 3.08 (s, 12H), 1.56 (m, J=7.2Hz, 4H), 1.31 (m, J=7.2Hz, 4H), 0.92 (t, J=7.2Hz, 6H); 166.00,165.18,46.40,35.77,30.23,20.28,13.92.
Mass spectrum: [M+H]
+295.
Show that this compound structure is correct.
The triazine derivative of embodiment 12, preparation formula I general structure (12)
With 5.16g (40mmol) N, N-two (2-methyl) propyl group amine and 0.69g (5mmol) salt of wormwood are dissolved in the 100ml water and join in the 500ml three-necked bottle, with 2.015g (10mmol) 6-chloro-2,4-two (N, the N-dimethyl) amino-1,3,5-triazines is dissolved in the tetrahydrofuran (THF), and this solution splashed in the three-necked bottle reaction 24 hours down of 80 ℃ of systems.Reaction product extracted with diethyl ether (60ml * 3), the alkali alumina column chromatography.Obtain colourless liquid 0.83g, productive rate 28.3% is the triazine derivative (12) of formula I general structure.
Ultimate analysis: molecular formula C
15H
30N
6Molecular weight 294
Theoretical value: C 61.19 H 10.27 N 28.54 measured values: C 61.22 H 10.40 N 28.29
Nucleus magnetic resonance: 3.35 (d, J=7.2Hz, 4H), 3.08 (s, 12H), 2.15 (m, J=7.2Hz, 2H), 0.86 (d, J=6.9Hz, 12H); 165.88,165.87,55.152,35.74,27.34,20.48.
Mass spectrum: [M+H]
+295.
Show that this compound structure is correct.
The triazine derivative of embodiment 13, preparation formula I general structure (13)
In the 500ml there-necked flask, add the 60ml mixture of ice and water, stir in the ice bath, be dissolved in 18.45g (100mmol) Cynuric Chloride in the 40ml acetone and pour there-necked flask into, splash into the ethylamine solution of 27g (200mol) 33% with constant pressure funnel, remove ice bath, splash into the aqueous solution 40ml that is dissolved with 10.6g (100mmol) yellow soda ash, drip off in 20 minutes, system is heated to 40-50 ℃, keeps the cooling system 5 minutes, filtration under diminished pressure, massive laundering is washed, and gets white solid 17.56g, and productive rate is 86.8%, be 6-chloro-2,4-diethylin-1,3,5-triazines.With 2.02g (20mmol) N, N-dipropylamine and 0.69g (5mmol) salt of wormwood is dissolved in the 50ml water and places a 250ml there-necked flask, with 2.015g (10mmol) 6-chloro-2,4-diethylin-1,3,5-triazines is dissolved in the 20ml tetrahydrofuran (THF), and this solution splashed into there-necked flask, system was reacted 36 hours down in 40 ℃, reaction product extracted with diethyl ether, column chromatography for separation.Obtain pale yellow oily liquid body 0.65g, productive rate is 24.4%, is the triazine derivative (13) of formula I general structure.
Ultimate analysis: molecular formula C
13H
26N
6Molecular weight 266
Theoretical value: C 58.61 H 9.84 N 31.55 measured values: C 58.64 H 9.67 N 31.68
Nucleus magnetic resonance: 4.70 (br, 2H), 3.36 (m, 8H), 1.60 (m, J=7.2Hz, 4H), 1.16 (t, J=7.2Hz, 6H), 0.89 (t, J=7.2Hz, 6H); 166.09,165.31,48.56,35.44,21.30,15.15,11.40.
Mass spectrum: [M+H]
+267.
Show that this compound structure is correct.
The triazine derivative of embodiment 14, preparation formula I general structure (14)
With 2.87g (30mmol) N, N-di-n-butyl amine and 0.69g (5mmol) salt of wormwood is dissolved in the 70ml water and places a 250ml there-necked flask, with 2.015g (10mmol) 6-chloro-2,4-diethylin-1,3,5-triazines is dissolved in the 20ml tetrahydrofuran (THF), and this solution splashed into there-necked flask, system was reacted 30 hours down in 60 ℃, reaction product extracted with diethyl ether, column chromatography for separation.Obtain colourless oil liquid 0.71g, productive rate is 24.1%, is the triazine derivative (14) of formula I general structure.
Ultimate analysis: molecular formula C
15H
30N
6Molecular weight 294
Theoretical value: C 61.19 H 10.27 N 28.54 measured values: C 60.98 H 10.04 N 28.56
Nucleus magnetic resonance: 4.61 (br, 2H), 3.47 (t, J=7.5Hz, 4H), 3.37 (m, J=7.2Hz, 4H), 1.55 (m, J=7.5Hz, 4H), 1.31 (m, J=7.5Hz, 4H), 1.16 (t, J=7.2Hz, 6H), 0.93 (t, J=7.2Hz, 6H); 166.10,165.25,46.38,35.45,30.22,20.21,15.19,13.88.
Mass spectrum: [M+H]
+295.
Show that this compound structure is correct.
The triazine derivative of embodiment 15, preparation formula I general structure (15)
With 2.58g (20mmol) N, N-two (2-methyl) propyl group amine and 0.69g (5mmol) salt of wormwood are dissolved in the 50ml water and place a 250ml there-necked flask, with 2.015g (10mmol) 6-chloro-2,4-diethylin-1,3,5-triazines is dissolved in the 15ml tetrahydrofuran (THF), and this solution splashed into there-necked flask, system was reacted 40 hours down in 80 ℃, reaction product extracted with diethyl ether, column chromatography for separation.Obtain colourless oil liquid 0.45g, productive rate is 15.3%, is the triazine derivative (15) of formula I general structure.
Ultimate analysis: molecular formula C
15H
30N
6Molecular weight 294
Theoretical value: C 61.19 H 10.27 N 28.54 measured values: C 61.19 H 10.18 N 28.42
Nucleus magnetic resonance: 4.65 (br, 2H), 3.36 (m, 8H), 2.11 (m, J=6.9Hz, 2H), 1.17 (t, J=7.2Hz, 6H), 1.31 (d, J=6.9Hz, 12H); 165.95,165.90,54.93,35.44,27.22,20.34,15.17.
Mass spectrum: [M+H]
+295.
Show that this compound structure is correct.
The triazine derivative of embodiment 16, preparation formula I general structure (16)
In two mouthfuls of bottles of 500ml, add the 60ml mixture of ice and water, ice bath stirs, and 18.45g (100mmol) Cynuric Chloride is dissolved in the 40ml acetone, and this acetone soln is poured in two mouthfuls of bottles, constant pressure funnel splashes into the ammonia soln of 13.6g (200mmol) 25%, remove ice bath, drip off the aqueous solution 40ml that is dissolved with 10.6g (100mmol) yellow soda ash in 20 minutes, system is heated to 40 ℃, reacted 5 minutes, the reaction product suction filtration, massive laundering, drying.Obtain white plates solid 10.876g, productive rate 98.9%.Be 6-chloro-2, the 4-diamino-1,3,5-triazines.With 3.03g (30mmol) N, N-dipropyl amine and 1.38g (10mmol) salt of wormwood is dissolved in the 100ml water and pours in the 500ml there-necked flask, with 2.18g (15mmol) 6-chloro-2, the 4-diaminostilbene, 3, the 5-triazine is dissolved in the 20ml tetrahydrofuran (THF), splashes into this solution in the there-necked flask and makes system in 90 ℃ of down reactions 30 hours, the reaction product extracted with diethyl ether, column chromatography for separation.Obtain white solid 1.03g, productive rate is 24.5%, is the triazine derivative (16) of formula I general structure.
Ultimate analysis: molecular formula C
9H
18N
6Molecular weight 210
Theoretical value: C 51.41 H 8.63 N 39.97 measured values: C 51.38 H 8.73 N 39.81
Nucleus magnetic resonance: 4.67 (br, 4H), 3.41 (t, J=7.2Hz, 4H), 1.58 (m, J=7.2Hz, 4H), 0.89 (t, J=7.2Hz, 6H); 167.31,166.98,48.41,21.08,11.29.
Mass spectrum: [M+H]
+211.
Show that this compound structure is correct.
The triazine derivative of embodiment 17, preparation formula I general structure (17)
With 3.87g (30mmol) N, N-two (2-methyl) propylamine and 1.035g (7.5mmol) salt of wormwood are dissolved in the 100ml water and pour in the 500ml there-necked flask, with 2.18g (15mmol) 6-chloro-2, the 4-diaminostilbene, 3, the 5-triazine is dissolved in the 20ml tetrahydrofuran (THF), splashes into this solution in the there-necked flask and makes system in 70 ℃ of down reactions 20 hours, the reaction product extracted with diethyl ether, column chromatography for separation.Obtain white solid 0.7g, productive rate is 19.6%, is the triazine derivative (17) of formula I general structure.
Ultimate analysis: molecular formula C
11H
22N
6Molecular weight 238
Theoretical value: C 55.43 H 9.30 N 35.26 measured values: C 55.55 H 9.33 N 35.27
Nucleus magnetic resonance: 4.70 (br, 4H), 3.31 (d, J=7.5Hz, 4H), 2.08 (m, J=6.9Hz, 2H), 0.86 (d, J=6.9Hz, 12H); 167.19,166.65,54.50,26.94,20.17.
Mass spectrum: [M+H]
+239.
Show that this compound structure is correct.
The triazine derivative of embodiment 18, preparation formula I general structure (18)
Be dissolved in 2.19g (30mmol) n-Butyl Amine 99 and 2.07g (15mmol) salt of wormwood in the 100ml frozen water and pour in the 500ml there-necked flask, 2.768g (15mmol) Cynuric Chloride is dissolved in the 25ml tetrahydrofuran (THF), and this solution poured in the there-necked flask, 0 ℃ was stirred 10 minutes down, being warming up to 50 ℃ stirred 10 minutes, the reaction product suction filtration, washing, drying.Obtain 6-chloro-2,4-two n-butyl amine base-1,3,5-triazines.With 2.58g (20mmol) N, N-dibutylamine and 1.035g (7.5mmol) salt of wormwood is dissolved in the 70ml water and pours in the 250ml there-necked flask, with 3.85g (15mmol) 6-chloro-2,4-two n-butyl amine bases-1,3, the 5-triazine is dissolved in the 15ml tetrahydrofuran (THF), splashes into this solution in the there-necked flask and makes system in 70 ℃ of down reactions 30 hours, the reaction product extracted with diethyl ether, column chromatography for separation.Obtain colourless oil liquid 2.02g, productive rate is 38.5%, is the triazine derivative (18) of formula I general structure.
Ultimate analysis: molecular formula C
19H
38N
6Molecular weight 350
Theoretical value: C 65.10 H 10.93 N 23.97 measured values: C 64.84 H 10.91 N 23.97
Nucleus magnetic resonance: 4.65 (br, 2H), 3.46 (t, J=7.5Hz, 4H), 3.33 (m, J=6.6Hz, 4H), 1.54 (m, J=7.2Hz, 8H), 1.34 (m, J=7.5Hz, 8H), 0.93 (t, J=7.2Hz, 12H); 166.22,165.22,46.46,40.38,32.15,30.25,20.24,20.08,13.89,13.74.
Mass spectrum: [M+H]
+351.
Show that this compound structure is correct.
The triazine derivative of embodiment 19, preparation formula V general structure
Add the 300ml mixture of ice and water in the 2L there-necked flask, flask places ice bath, mechanical stirring.The 200ml acetone that will be dissolved with 92.3g (0.5mol) cyanuric chloride pours in this mixture of ice and water, makes cyanuric chloride muddy suspension.In 30min, drip 33% aqueous methylamine solution 93.9g (1mol), remove ice bath, in 1.5 hours, drip off the 200ml aqueous solution that is dissolved with 53g (0.5mol) yellow soda ash by constant pressure funnel.Dropwise the afterreaction system and be heated to 40～50 ℃, keep this temperature several minutes after, cooling reaction system, filtration under diminished pressure, wash filter residue with massive laundering, get white solid, thorough drying, get the 86.4g white powder, productive rate is 99.6%, is compound shown in the intermediate formula IV.
Formula IV
In the 500ml there-necked flask, add compound shown in 34.7g (0.2mol) the formula IV, 38.7g N, N-dibutylamine (0.3mol), 300ml DMF, 12.9g N is added in 100 ℃ of heating of oil bath after 24 hours, and N-dibutylamine (0.1mol) continues 100 ℃ of reactions 12 hours.Cooling adds 600ml water in reaction solution, add the aqueous solution that contains 89g sodium hydroxide (0.2mol), makes system pH=9.0.Add extracted with diethyl ether (800ml * 2), organic phase merges, saturated common salt water washing (300ml * 1), anhydrous sodium sulfate drying.Dried organic phase concentrates and to be spin-dried for, sorrel oily matter, sample on the liquid, PE/EA makes eluent, column chromatography, after use ethyl acetate/methanol instead and make eluent, obtain the triazine derivative shown in the formula V, be sorrel oily matter 31.2g, productive rate 59%.
Ultimate analysis: molecular formula C
12H
24N
6, molecular weight 266
Theoretical value: C 57.11 H 9.59 N 33.3; Measured value: C 58.31 H 9.77 N 31.29
Nucleus magnetic resonance: 4.96 (s, 2H), 3.49 (t, J=7.1Hz, 4H), 2.89 (d, J=5.0Hz, 6H), 1.56 (m, J=7.0Hz, 4H), 1.33 (m, J=7.3Hz, 4H), 0.93 (t, J=7.3Hz, 6H); 166.70,165.11,46.23,30.14,27.44,20.21,13.94.
Mass spectrum: 266[M]
+(52), 237 (37), 223 (60), 181 (100), 167 (55).
Show that this compound structure is correct.
The triazine derivative of embodiment 20, preparation formula V general structure
In the 2L there-necked flask, add 300ml frozen water-dichloromethane mixture, place under-10 ℃ mechanical stirring.The 150ml methylene dichloride that will be dissolved with 92.3g (0.5mol) cyanuric chloride pours in this mixture of ice and water, makes cyanuric chloride muddy suspension.In 30min, drip 15% aqueous methylamine solution 516.7g (2.5mol), remove ice bath, in 1.5 hours, drip off the 200ml aqueous solution that is dissolved with 53g (0.5mol) yellow soda ash by constant pressure funnel.Dropwise the afterreaction system and be heated to 40～50 ℃, keep this temperature several minutes after, cooling reaction system, filtration under diminished pressure, wash filter residue with massive laundering, get white solid, thorough drying, get the 86.4g white powder, productive rate is 99.6%, is compound shown in the intermediate formula IV.
In the 50ml two-mouth bottle, add successively compound shown in the formula IV (6.94g, 0.04mol), dimethyl sulphoxide solution 30ml, (2.58g, 0.02mol), oil bath heating control reaction temperature is 100 ℃ to diisobutylamine.Along with the carrying out of reaction, reaction solution is muddy, and solution colour fades to safran, reaction 24h stopped reaction, cooling.In reaction solution, add 60ml water, add the aqueous solution that contains 0.8g sodium hydroxide, regulate pH=9.With extracted with diethyl ether (80ml * 2), organic phase is with saturated common salt water washing (30ml * 1), after anhydrous sodium sulfate drying [have in the extraction process solid insoluble] always.Dried organic phase is revolved to steam and is removed ether, and pneumatic pump revolves steaming removes (bath temperature are greater than 62 ℃) such as unreacted high boiling point raw materials.Get safran oily matter, sample column chromatography on the wet method (PE/EA eluent) gets safran oily matter 4.02g, and productive rate is 75.6%, is the triazine derivative of formula V general structure.
Ultimate analysis: molecular formula C
13H
26N
6, molecular weight 266
Theoretical value: C 58.61 H 9.84 N 31.55 measured values: C 58.63 H 9.93 N 31.51
Nucleus magnetic resonance: 4.72 (s, 2H), 3.35 (d, J=7.2Hz, 4H), 2.89 (d, J=5.0Hz, 6H), 2.11 (m, J=6.7Hz, 2H), 0.87 (d, J=6.7Hz, 12H); 166.53,165.79,54.86,27.47,27.19,20.38.
Mass spectrum: 266[M]
+(10), 223 (85), 167 (100).
Show that this compound structure is correct.
The triazine derivative of embodiment 21, preparation formula V general structure
In the 2L there-necked flask, add 300ml frozen water-acetonitrile mixture, place under-20 ℃ mechanical stirring.The 150ml acetonitrile that will be dissolved with 92.3g (0.5mol) cyanuric chloride pours in this mixture of ice and water, makes cyanuric chloride muddy suspension.In 30min, drip 50% aqueous methylamine solution 15.5g (0.25mol), remove ice bath, in 1.5 hours, drip off the 200ml aqueous solution that is dissolved with 138.21g (1mol) salt of wormwood by constant pressure funnel.Dropwise the afterreaction system and be heated to 15 ℃, keep this temperature several minutes after, cooling reaction system, filtration under diminished pressure, wash filter residue with massive laundering, get white solid, thorough drying, get the 43.2g white powder, productive rate is 49.5%, is compound shown in the intermediate formula IV.
In the 50ml two-mouth bottle, add successively compound shown in the formula IV (3.47g, 0.02mol), (6.06g, 0.06mol), tetrahydrofuran solution 30ml, oil bath heating control reaction temperature is 50 ℃ to di-n-propylamine.Along with the carrying out of reaction, reaction solution is muddy, and solution colour fades to safran, reaction 12h stopped reaction, cooling.In reaction solution, add 60ml water, add the aqueous solution that contains 0.8g sodium hydroxide, regulate pH=9.With extracted with diethyl ether (80ml * 2), organic phase is with saturated common salt water washing (30ml * 1), after anhydrous sodium sulfate drying [have in the extraction process solid insoluble] always.Dried organic phase is revolved to steam and is removed ether, and pneumatic pump revolves steaming removes (bath temperatures＞62 degree) such as unreacted high boiling point raw materials.Get safran oily matter, sample column chromatography on the wet method (PE/EA eluent) gets safran oily matter 3.68g, and productive rate is 77.3%, is the triazine derivative of formula V general structure.
Ultimate analysis: molecular formula C
11H
22N
6Molecular weight 238
Theoretical value: C 55.43 H 9.30 N 35.26 measured values: C 55.31 H 9.27 N 35.15
Nucleus magnetic resonance: 4.85 (s, 2H), 3.45 (t, J=7.3Hz, 4H), 2.89 (d, J=5.0Hz, 6H), 1.60 (m, J=7.4Hz, 4H), 5.97 (t, J=7.4Hz, 6H); 166.74,165.20,48.47,27.45,21.25,11.47.
Mass spectrum: 238[M]
+(47), 209 (100), 195 (26), 167 (95)
Show that this compound structure is correct.
The triazine derivative of embodiment 22, preparation formula V general structure
In the 2L there-necked flask, add the 300ml mixture of ice and water, place under 0 ℃ mechanical stirring.The 200ml acetone that will be dissolved with 92.3g (0.5mol) cyanuric chloride pours in this mixture of ice and water, makes cyanuric chloride muddy suspension.In 30min, drip 33% aqueous methylamine solution 93.9g (1mol), remove ice bath, in 1.5 hours, drip off the 200ml aqueous solution that is dissolved with 84g (1mol) sodium bicarbonate by constant pressure funnel.Dropwise the afterreaction system and be heated to 50 ℃, keep this temperature several minutes after, cooling reaction system, filtration under diminished pressure, wash filter residue with massive laundering, get white solid, thorough drying, get the 86.4g white powder, productive rate is 99.6%, is compound shown in the intermediate formula IV.
In the 50ml two-mouth bottle, add successively compound shown in the formula IV (3.47g, 0.02mol), (1.74g, 0.02mol), oil bath heating control reaction temperature is 80 ℃ for DMF solution 30ml, N-methyl n-Butyl Amine 99.Along with the carrying out of reaction, reaction solution fades to redness by white particle suspension, reaction 12h stopped reaction, cooling.In reaction solution, add 60ml water, add the aqueous solution that contains 0.8g sodium hydroxide, regulate pH=9.With extracted with diethyl ether (80ml * 2,50ml * 1), organic phase is with saturated common salt water washing (30ml * 1), after anhydrous sodium sulfate drying [have in the extraction process solid insoluble] always.Dried organic phase is revolved to steam and is removed ether, and pneumatic pump revolves steaming removes (bath temperatures＞62 degree) such as unreacted high boiling point raw materials.Get orange oily matter, sample column chromatography on the wet method (PE/EA eluent) gets orange oily matter 3.63g, and productive rate is 81.3%, is the triazine derivative of formula V general structure.
Ultimate analysis: molecular formula C
10H
18N
6, molecular weight 224
Theoretical value: C 54.03 H 8.16 N 37.81; Measured value: C 58.23 H 9.74 N 31.40
Nucleus magnetic resonance: 5.00 (s, 2H), 3.56 (t, J=6.86Hz, 2H), 3.06 (s, 3H), 2.90 (d, J=5.52Hz, 6H), 1.55 (m, J=6.98Hz, 2H), 1.33 (m, J=7.35Hz, 2H), 0.93 (t, J=7.29Hz, 3H); 166.65,165.36,47.81,33.95,29.55,27.48,20.03,13.95.
Mass spectrum: 224[M]
+(40), 195 (45), 181 (100), 167 (26).
Show that this compound structure is correct.
The triazine derivative of embodiment 23, preparation formula V general structure
In the 2L there-necked flask, add 300ml frozen water-trichloromethane mixture, place under 0 ℃ mechanical stirring.The 200ml trichloromethane that will be dissolved with 92.3g (0.5mol) cyanuric chloride pours in this mixture of ice and water, makes cyanuric chloride muddy suspension.In 30min, drip 33% aqueous methylamine solution 93.9g (1mol), remove ice bath, in 1.5 hours, drip off the 200ml aqueous solution that is dissolved with 210g (2.5mol) sodium bicarbonate by constant pressure funnel.Dropwise the afterreaction system and be heated to 50 ℃, keep this temperature several minutes after, cooling reaction system, filtration under diminished pressure, wash filter residue with massive laundering, get white solid, thorough drying, get the 86.4g white powder, productive rate is 99.6%, is compound shown in the intermediate formula IV.
In the 50ml two-mouth bottle, add successively compound shown in the formula IV (3.47g, 0.02mol), diethyl ether solution 30ml, (7.3g, 0.1mol), control reaction temperature is 30 ℃ to diethylamine.Along with the carrying out of reaction, reaction solution is muddy, and solution colour fades to orange, reaction 2h stopped reaction, cooling.In reaction solution, add 60ml water, add the aqueous solution that contains 0.8g sodium hydroxide, regulate pH=9.With extracted with diethyl ether (80ml * 2), organic phase is with saturated common salt water washing (30ml * 1), after anhydrous sodium sulfate drying [have in the extraction process solid insoluble] always.Dried organic phase is revolved to steam and is removed ether, and pneumatic pump revolves and steams (bath temperatures＞62 degree such as removing unreacted high boiling point raw material.Get orange oily matter, sample column chromatography on the wet method (PE/EA eluent) gets orange oily matter 2.56g, and productive rate is 61.0%, is the triazine derivative of formula V general structure.
Ultimate analysis: molecular formula C
9H
18N
6Molecular weight 210
Theoretical value: C 51.41 H 8.63 N 39.97 measured values: C 51.33 H 8.51 N 40.01
Nucleus magnetic resonance: 4.89 (s, 2H), 3.55 (q, J=6.4Hz, 4H), 2.90 (d, J=4.9Hz, 6H), 1.14 (t, J=6.4Hz, 6H); 166.75,164.63,40.68,27.39,13.27.
Mass spectrum: 210[M]
+(50), 195 (23), 181 (100), 167 (26).
Show that this compound structure is correct.
The triazine derivative of embodiment 24, preparation formula V general structure
In the 2L there-necked flask, add the 300ml mixture of ice and water, place under 0 ℃ mechanical stirring.The 200ml acetone that will be dissolved with 92.3g (0.5mol) cyanuric chloride pours in this mixture of ice and water, makes cyanuric chloride muddy suspension.In 30min, drip 33% aqueous methylamine solution 93.9g (1mol), remove ice bath, in 1.5 hours, drip off the 200ml aqueous solution that is dissolved with 40g (1mol) sodium hydroxide by constant pressure funnel.Dropwise the afterreaction system and be heated to 50 ℃, keep this temperature several minutes after, cooling reaction system, filtration under diminished pressure, wash filter residue with massive laundering, get white solid, thorough drying, get the 86.4g white powder, productive rate is 99.6%, is compound shown in the intermediate formula IV.
In the 50ml two-mouth bottle, add successively compound shown in the formula IV (3.47g, 0.02mol), DMF solution 30ml, triethylamine (1.82g, 0.018mol), (2.83g, 0.018mol), oil bath heating control reaction temperature is 150 ℃ to two n-amylamines.Along with the carrying out of reaction, reaction solution is muddy, and solution colour fades to sorrel, reaction 36h stopped reaction, cooling.In reaction solution, add 60ml water, add the aqueous solution that contains 0.8g sodium hydroxide, regulate pH=9.With extracted with diethyl ether (80ml * 2), organic phase is with saturated common salt water washing (30ml * 1), after anhydrous sodium sulfate drying [have in the extraction process solid insoluble] always.Dried organic phase is revolved to steam and is removed ether, pneumatic pump revolves steaming removes (bath temperatures＞62 degree) such as unreacted high boiling point raw materials, get sorrel oily matter, sample column chromatography on the wet method (PE/EA eluent), get red oil 3.08g, productive rate is 52.4%, the triazine derivative of formula V general structure.
Ultimate analysis: molecular formula C
15H
30N
6Molecular weight 294
Theoretical value: C 61.19 H 10.27 N 28.54 measured values: C 60.90 H 10.09 N 28.51
Nucleus magnetic resonance: 4.90 (s, 2H), 3.47 (t, J=7.3Hz, 4H), 2.89 (d, J=5.0Hz, 6H), 1.56 (m, J=7.2Hz, 4H), 1.33 (m, J=6.2Hz, 8H), 0.89 (t, J=6.9Hz, 6H); 166.69,165.08,46.56,29.24,27.64,27.45,22.50,14.06.
Mass spectrum: 294[M]
+(52), 237 (50), 181 (100), 167 (40)
Show that this compound structure is correct.
Embodiment 25, the indoor insecticidal activity assay of a kind of triazine derivative
Test target: Nilaparvata lugen (brown planthopper) (Nilaparvata legen), mythimna separata (Mythima separata), red spider (Tetranychus cinnabarnus), aphis craccivora (Aphis medicagini).Above worm kind is the indoor worm kind of throughout the year for many generations raising.
Chemicals treatment: take by weighing the former medicine of certain mass with analytical balance (0.0001g), add the solvent (DMF) that contains 0.1% tween-80, be mixed with 5% preparation.Take by weighing the preparation of certain mass, the adding distil water dilution is mixed with the soup of measuring desired concn.Estimate SOP (sterilant volume) according to the initiative pesticide bioactivity, general sieve concentration is selected 500mg/L.
Paddy rice brown paddy plant hopper screening---the quantitative spray method of culture dish seedling worm
The paddy rice seedling is fixed in the culture dish with white quartz sand, connects and use CO
2Anaesthetize 3 mid-term in age nymph, place under the POTTER spray tower spraying.The spraying back covers with the transparent plastics cup, is put in the observation ward behind the mark.Test repeats 4 times.Check result behind the 72h.Touch polypide with writing brush, reactionlessly be considered as dead worm.With SD-1750 and blank CK is contrast.
The mythimna separata screening---soak the seedling feeding method
Leaf of Semen Maydis is fully soaked into the back dry in the shade naturally in soup, put into culture dish, connect 3 mid-term in age larva, add a cover mark and be placed in the observation ward.Test repeats 4 times.Check result behind the 72h.Touch polypide with writing brush, reactionlessly be considered as dead worm.With SD-1750 and blank CK is contrast.
Carmine spider mite screening---pickling process
The broad bean blade is broken into the leaf dish, and the back side is placed on the fritter cotton up, places in the plastic culture dish, adds less water, connects carmine spider mite and becomes mite.Treat into mite after stablizing on the blade, blade is fully inhaled defoliation sheet surface water droplet with thieving paper rapidly behind the infiltration 5s in soup, place again on the cotton, air-dry.Test repeats 4 times.Check result behind the 72h.With pyridaben and blank CK is contrast.
Aphis craccivora screening---pickling process
If the broad bean blade is cut off two ends, and the back side is placed on the fritter cotton up, places in the plastic culture dish, adds less water, connects aphis craccivora and becomes aphid to produce aphid.Remove into aphid behind the 24h, continue behind the cultivation 2d blade behind the abundant 5s of infiltration, to be placed on the cotton natural airing again in soup.Check result behind the 24h.With carbosulfan and blank CK is contrast.
Test statistics and advance the sieve standard:
Add up the dead borer population of each processing and the borer population of living, the calculating mortality ratio (Abbott ' the s formula).
Table 1, the general sieve result of compound insecticidal activity (mortality ratio, %)
| Compound number | Concentration (mg/L) | Planthopper (%) | Mythimna separata (%) | Red spider (%) | Aphid (%) |
| 1 | 500 | 0 | 0 | 0 | 0 |
| 2 | 500 | 0 | 0 | 0 | 0 |
| 3 | 500 | 0 | 0 | 0 | 0 |
| 4 | 500 | 0 | 0 | 0 | 0 |
| 5 | 500 | 0 | 0 | 0 | 0 |
| 6 | 500 | 0 | 0 | 0 | 0 |
| 7 | 500 | 0 | 0 | 0 | 0 |
| 8 | 500 | 0 | 0 | 0 | 0 |
| 9 | 500 | 0 | 0 | 0 | 0 |
| 10 | 500 | 0 | 0 | 0 | 0 |
| 11 | 500 | 0 | 0 | 0 | 0 |
| 12 | 500 | 0 | 0 | 0 | 0 |
| 13 | 500 | 0 | 0 | 100 | 0 |
| 14 | 500 | 0 | 0 | 0 | 0 |
| 15 | 500 | 0 | 0 | 100 | 0 |
| 16 | 500 | 0 | 0 | 100 | 0 |
| SD-1750 | 100 | 100 | 100 | ||
| Pyridaben | 50 | 100 | |||
| Carbosulfan | 20 | 100 |
Table 2, the general sieve result of compound insecticidal activity (mortality ratio, %)
Claims (20)
1. triazine derivative shown in the formula I,
(formula I)
In the described formula I general structure, R
1, R
2, R
3, R
4, R
5, R
6All being selected from H and backbone c atoms number is C
1-C
6Alkyl.
2. triazine derivative according to claim 1 is characterized in that: in the described formula I general structure, and R
1-R
6All be selected from hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-pentyl, 2-methyl butyl, 3-methyl butyl, n-hexyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3, any one in 3-dimethylbutyl, 1-methyl amyl, 2-methyl amyl, 3-methyl amyl or the 4-methyl amyl; In preferred hydrogen, methyl, n-propyl, sec.-propyl, normal-butyl and the 3-methyl-propyl any one.
3. a method for preparing the described triazine derivative of claim 1 comprises the steps: secondary amine shown in Cynuric Chloride, alkali and the formula II is reacted, and obtains described triazine derivative;
(formula II)
In the described formula II general structure, R
1, R
2, R
3, R
4, R
5, R
6All being selected from H and backbone c atoms number is C
1-C
6Alkyl.
4. method according to claim 3 is characterized in that: the mol ratio of the secondary amine shown in described Cynuric Chloride and the formula II general structure is 1: 1-1: 20, and preferred 1: 3.
5. according to claim 3 or 4 described methods, it is characterized in that: described temperature of reaction is 0-150 ℃, preferred 80 ℃; Reaction times is 0-100 hour, preferred 24 hours.
6. according to the arbitrary described method of claim 3-5, it is characterized in that: described alkali is selected from least a in yellow soda ash, salt of wormwood, sodium bicarbonate and the sodium hydroxide, preferred yellow soda ash;
Described reaction medium is selected from least a in acetone, methylene dichloride, trichloromethane, ether, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), dioxane and the acetonitrile, preferred tetrahydrofuran (THF).
7. according to the arbitrary described method of claim 3-6, it is characterized in that: the mol ratio of described alkali and described Cynuric Chloride is 10: 1-1: 2, and preferred 3: 1.
8. a method for preparing the described triazine derivative of claim 1 comprises the steps: primary amine shown in Cynuric Chloride, alkali and the formula III is reacted, and obtains described triazine derivative;
H
2N-R
(formula III)
In the described formula III general structure, R
1, R
2, R
3, R
4, R
5, R
6All being selected from H and backbone c atoms number is C
1-C
6Alkyl.
9. method according to claim 8 is characterized in that: the mol ratio of the primary amine shown in described Cynuric Chloride and the formula III general structure is 1: 1-1: 20, and preferred 1: 3.
10. according to Claim 8 or 9 described methods, it is characterized in that: described temperature of reaction is 0-150 ℃, preferred 80 ℃; Reaction times is 0-100 hour, preferred 24 hours.
11. arbitrary according to Claim 8-10 described method, it is characterized in that: described alkali is selected from any one in yellow soda ash, salt of wormwood, sodium bicarbonate and the sodium hydroxide, preferred yellow soda ash; Described reaction medium is selected from acetone, methylene dichloride, trichloromethane, ether, tetrahydrofuran (THF), N, and is at least a in dinethylformamide, dioxane and the acetonitrile, preferred tetrahydrofuran (THF).
12. arbitrary according to Claim 8-11 described method is characterized in that: the mol ratio of described alkali and described Cynuric Chloride is 10: 1-1: 2, preferred 3: 1.
13. one kind prepares the described R of claim 1
3Be methyl and R
4Method for the triazine derivative of H may further comprise the steps:
1) under-20 ℃ of-10 ℃ of conditions, the reaction of cyanuric chloride and aqueous methylamine solution is finished, add alkali then and continue reaction after 60-180 minute, be warming up to 15-80 ℃, obtain intermediate formula V compound;
Wherein, described alkali is yellow soda ash, salt of wormwood, sodium bicarbonate or sodium hydroxide;
Formula V
2) be R with described intermediate formula V compound and substituting group
1And R
2Diamines 30-150 ℃ of reaction, obtain described triazine derivative; Wherein, described R
1And R
2Be C
2-C
6Alkyl.
14. method according to claim 13 is characterized in that: in the described step 1), the temperature of reaction of cyanuric chloride and aqueous methylamine solution is 0 ℃ of ice bath; The reaction times of cyanuric chloride and aqueous methylamine solution is 5-120 minute;
Described step 2) temperature of reaction is preferably 100 ℃; Intermediate formula V compound and substituting group are R
1And R
2Reaction times of diamines be 2h-36h.
15. according to claim 13 or 14 described methods, it is characterized in that: in the described step 1), the mass percent concentration of aqueous methylamine solution is 15%-50%, preferred 33%; The mol ratio of cyanuric chloride and aqueous methylamine solution is 2: 1-1: 5, and preferred 1: 2; The mol ratio of alkali and cyanuric chloride is 1: 1-1: 5, and preferred 1: 2;
Described step 2) in, intermediate formula II compound and described substituting group are R
1And R
2The mol ratio of diamines be 2: 1-1: 5, preferred 1: 1.
16. according to the arbitrary described method of claim 13-15, it is characterized in that: the solvent of described step 1) is selected from least a in acetone, methylene dichloride, trichloromethane, ether, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), dioxane and the acetonitrile, preferred acetone; Described alkali is yellow soda ash; Described step 2) solvent is selected from acetone, methylene dichloride, trichloromethane, ether, tetrahydrofuran (THF), N, any one in dinethylformamide, dioxane and the acetonitrile, preferred N, dinethylformamide.
17. with the described triazine derivative of claim 1 is the sterilant of activeconstituents.
18. sterilant according to claim 17 is characterized in that: the target worm of described sterilant is at least a in planthopper, mythimna separata, red spider and the aphid.
19. the application of the described triazine derivative of claim 1 in the preparation sterilant.
20. application according to claim 19 is characterized in that: the target worm of described sterilant is at least a in planthopper, mythimna separata, red spider and the aphid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910084470A CN101885707B (en) | 2009-05-15 | 2009-05-15 | Triazine derivative and preparation method thereof as well as new application as insecticide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910084470A CN101885707B (en) | 2009-05-15 | 2009-05-15 | Triazine derivative and preparation method thereof as well as new application as insecticide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101885707A true CN101885707A (en) | 2010-11-17 |
| CN101885707B CN101885707B (en) | 2012-08-29 |
Family
ID=43071822
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910084470A Expired - Fee Related CN101885707B (en) | 2009-05-15 | 2009-05-15 | Triazine derivative and preparation method thereof as well as new application as insecticide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101885707B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102442960A (en) * | 2011-09-30 | 2012-05-09 | 武汉工程大学 | Cyanuric chloride derivative as well as preparation method and application thereof |
| US20120295911A1 (en) * | 2010-11-29 | 2012-11-22 | Galleon Pharmaceuticals, Inc. | Novel Compounds and Compositions for Treatment of Breathing Control Disorders or Diseases |
| WO2013181217A3 (en) * | 2012-05-29 | 2014-02-06 | Galleon Pharmaceuticals, Inc. | Novel compounds and compositions for treatment of breathing control disorders or diseases |
| US9351972B2 (en) | 2010-11-29 | 2016-05-31 | Galleon Pharmaceuticals, Inc. | Compounds as respiratory stimulants for treatment of breathing control disorders or diseases |
| CN110615770A (en) * | 2018-07-13 | 2019-12-27 | 四川大学 | CO useful for Click reactions2Responsive compounds and methods of making the same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2150565B (en) * | 1983-12-02 | 1987-08-26 | Ciba Geigy Ag | Pesticidal acylamino-s-triazines |
| TW401406B (en) * | 1993-07-20 | 2000-08-11 | Nissan Chemiacl Ind Ltd | The alkylation method of the triazine derivitives |
| FR2818126B1 (en) * | 2000-12-18 | 2003-02-07 | Oreal | PHOTOSTABLE FILTERING COMPOSITION CONTAINING A DERIVATIVE OF 1,3,5, -TRIAZINE, A DERIVATIVE OF DIBENZOYLMETHANE AND A COMPOUND 4,4-DIARYLBUTADIENE |
| CN1166648C (en) * | 2001-11-09 | 2004-09-15 | 复旦大学 | Process for preparing insecticide 'Huanbingmazhen' |
| CN101481358A (en) * | 2008-01-11 | 2009-07-15 | 中国科学院化学研究所 | Triazine derivatives, as well as preparation method and application thereof |
-
2009
- 2009-05-15 CN CN200910084470A patent/CN101885707B/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120295911A1 (en) * | 2010-11-29 | 2012-11-22 | Galleon Pharmaceuticals, Inc. | Novel Compounds and Compositions for Treatment of Breathing Control Disorders or Diseases |
| US9162992B2 (en) | 2010-11-29 | 2015-10-20 | Galleon Pharmaceuticals, Inc. | Compounds and compositions for treatment of breathing control disorders or diseases |
| US9351972B2 (en) | 2010-11-29 | 2016-05-31 | Galleon Pharmaceuticals, Inc. | Compounds as respiratory stimulants for treatment of breathing control disorders or diseases |
| AU2011336764B2 (en) * | 2010-11-29 | 2017-02-23 | Galleon Pharmaceuticals, Inc. | Novel compounds as respiratory stimulants for treatment of breathing control disorders or diseases |
| CN102442960A (en) * | 2011-09-30 | 2012-05-09 | 武汉工程大学 | Cyanuric chloride derivative as well as preparation method and application thereof |
| CN102442960B (en) * | 2011-09-30 | 2014-12-24 | 武汉工程大学 | Cyanuric chloride derivative as well as preparation method and application thereof |
| WO2013181217A3 (en) * | 2012-05-29 | 2014-02-06 | Galleon Pharmaceuticals, Inc. | Novel compounds and compositions for treatment of breathing control disorders or diseases |
| CN104602694A (en) * | 2012-05-29 | 2015-05-06 | 加林制药公司 | Novel compounds and compositions for treatment of breathing control disorders or diseases |
| CN110615770A (en) * | 2018-07-13 | 2019-12-27 | 四川大学 | CO useful for Click reactions2Responsive compounds and methods of making the same |
| CN110615770B (en) * | 2018-07-13 | 2020-11-03 | 四川大学 | CO useful for Click reactions2Responsive compounds and methods of making the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101885707B (en) | 2012-08-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102015679B (en) | 1-substituted pyridyl-pyrazolyl amide compounds and uses thereof | |
| CN101935291B (en) | Cyano phthalic diamide compounds, preparation method thereof and use thereof as agricultural chemical pesticide | |
| CN101885707B (en) | Triazine derivative and preparation method thereof as well as new application as insecticide | |
| CN104628722B (en) | A kind of banisterine amides compound and its preparation method and application | |
| CN103172512A (en) | Cajanin compound with similar structures, as well as preparation method and application thereof | |
| CN103664808B (en) | A kind of aryl 3-triazole compounds containing chlorocyclopropane and preparation method thereof and application | |
| CN101659655A (en) | Pyrazole amide derivative and application thereof | |
| CN101558758A (en) | L-alpha-amino acid ester contained Z-configuration anabasine pesticide and preparation method thereof | |
| CN103044431A (en) | Novel preparation method of penoxsulam | |
| CN100432068C (en) | Alkynyl thiofuran compound and its prepn and application | |
| CN109400568B (en) | 7-aryloxy acetoxyl isoflavone derivative and application thereof in pesticides | |
| CN101889577B (en) | Use of bishydrazide compounds as herbicide | |
| CN101884329B (en) | Use of triazine derivatives as bactericide | |
| CN106188032A (en) | A kind of preparation method of Diacloden | |
| CN108640871B (en) | Fluorine-containing pyridine piperazine urea compound and application thereof | |
| CN114249692B (en) | 2-imidazole benzamide active compound for preventing and treating wheat take-all and wheat stem basal rot | |
| CN108250156B (en) | Cinnamylate oxadiazine derivative and preparation method and application thereof | |
| CN103130796B (en) | A kind of 3-t-butylpyrazol amides and application thereof | |
| CN101481358A (en) | Triazine derivatives, as well as preparation method and application thereof | |
| CN102584667B (en) | Arylpyrrole compound with biological activity and preparation method thereof | |
| CN105254625B (en) | One kind class compound of yl-benzamide containing chloro-thiazole and its application | |
| CN102285966A (en) | 3-fluoro-5-chloropyridyl pyrazolecarboxamide compound and application thereof | |
| CN105732587B (en) | 6- substituted pyrimidyl quianzolinones and application thereof | |
| CN103709175B (en) | The one-step synthesis of the chloro-3H-oxazole of 6-also [4,5-b] pyridin-2-ones | |
| CN101759649A (en) | Benzimidazole amide bactericide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120829 Termination date: 20130515 |