CN100436419C - Alkali metal salt of 6-substituted amino-3,5-dihalogeno-2-pyridol and its prepn and application - Google Patents

Alkali metal salt of 6-substituted amino-3,5-dihalogeno-2-pyridol and its prepn and application Download PDF

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CN100436419C
CN100436419C CNB2005100607782A CN200510060778A CN100436419C CN 100436419 C CN100436419 C CN 100436419C CN B2005100607782 A CNB2005100607782 A CN B2005100607782A CN 200510060778 A CN200510060778 A CN 200510060778A CN 100436419 C CN100436419 C CN 100436419C
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pyridol
alkali metal
metal salt
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dihalo
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CN1931843A (en
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徐振元
郑辉
刘运奎
许丹倩
吴庆安
杜晓华
沈寅初
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Zhejiang University of Technology ZJUT
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Abstract

The present invention is alkali metal salt of 6-substituted amino-3, 5-dialogeno-2-pyridinol as the intermediate for synthesizing O-(6-amino-2-pyridyl) thiophosphate or phosphate derivative and its preparation process and application. The intermediate 6-substituted amino-3, 5-dialogeno-2-pyridinol is applied in preparing O-(6-amino-2-pyridyl) thiophosphate or phosphate derivative with high pesticidal activity, especially on aphid and armyworm, low toxicity, environment friendship, no harm to crop and great development foreground.

Description

A kind of 6-substituted amido-3,5-dihalo-2-pyridol an alkali metal salt and preparation thereof and application
(1) technical field
The present invention relates to a kind of 6-substituted amido-3,5-dihalo-2-pyridol an alkali metal salt and its production and application.
(2) background technology
Current, along with the development of agricultural modernization and people to the pay attention to day by day of ecotope, need constantly provide effective, consumption is low, to crop and environment low toxicity even harmless novel pesticide, to promote the coordinated development of agricultural modernization and Man ﹠ Nature environment.
Known O-(many halogen of 2-pyridyl) phosphorothioate derivative is that sterilant is effective.The Chlorpyrifos 94 of being developed by Dow Chemical Co. as nineteen sixty-five is exactly a kind of efficient, wide spectrum, and the organophosphorus desinsection of safety, miticide is one of at present global most widely used five kinds of sterilants.In addition, the chlorpyrifos_methyl of being developed by Dow Chemical Co. equally is another kind of broad spectrum pesticide.
In recent years, a large amount of uses of riskiest pesticide have caused the concern of the Chinese government to the negative impact that environment causes.Chlorpyrifos 94 belongs to one of kind of national encourage growth at present, and present annual requirement just increases with 38.7% amplitude.But, be that the pesticide species of sterilant is more single with O-(many halogen of 2-pyridyl) phosphorothioate derivative at present, in usefulness two kinds of Chlorpyrifos 94 and chlorpyrifos_methyls are only arranged.
(3) summary of the invention
The present invention promptly is to be the single deficiency of pesticide species of sterilant with O-(many halogen of 2-pyridyl) phosphorothioate derivative at present in order to overcome, introduce nitrogen-containing group for 6 at many halogen of 2-pyridol, provide a class more efficient, low toxicity, the synthetic intermediate 6-substituted amido-3 of the pesticide new variety of wide spectrum---a class O-(6-amido-2-pyridyl) thiophosphatephosphorothioate and phosphate derivative, 5-dihalo-2-pyridol an alkali metal salt and its production and application.
For reaching goal of the invention the technical solution used in the present invention be:
The intermediate 6-substituted amido-3 of a kind of preparation O-(6-amido-2-pyridyl) thiophosphatephosphorothioate or phosphate derivative, 5-dihalo-2-pyridol an alkali metal salt, structure is suc as formula shown in (IV):
Figure C20051006077800061
In the formula (IV), R 1, R 2Be group identical or inequality, hydrogen or C respectively do for oneself 1～C 6Alkyl or C 5～C 6Cyclic alkyl or benzyl or C 6～C 7Aryl; Perhaps R 1, R 2Become ring with N, R when becoming ring 1NR 2Represent Pyrrolidine base or hexahydropyridine base or morpholinyl or imidazolyl or connect triazolyl or 1,3,4-triazolyl; X is a halogen; E is hydrogen or halogen or cyano group; B is potassium or sodium.
Preferably, R 1, R 2Hydrogen or C respectively do for oneself 1～C 6Alkyl, perhaps R 1, R 2Become ring with N, R when becoming ring 1NR 2The amido of representative is a Pyrrolidine, imidazoles, and pyrazoles connects triazole, and 1,3,4-triazole, hexahydropyridine, morpholine, 1,4-Yi oxazine, perhaps R 1NR 2The amido of representative is a benzylamine, aniline, methylphenylamine, 4-chloroaniline, 2,4 dichloro aniline, 4-fluoroaniline, 4-monomethylaniline and 4-5-trifluoromethylaniline; X is a chlorine; E is a hydrogen; B is a sodium.
Described 6-substituted amido-3,5-dihalo-2-pyridol an alkali metal salt makes as follows: by the many halo 2-pyridol of structural formula shown in (II) with suc as formula the aminated compounds shown in (III) with 1: 1～10 amount of substance ratio, at the same time in the organic solvent of dissolution type (II) and formula (III), acid binding agent exists down, in room temperature to solvent boiling point temperature range internal reaction 5～40 hours, the gained reactant is handled suc as formula the 6-substituted amido-3 shown in (IV) through NaOH or KOH, 5-dihalo-2-pyridol an alkali metal salt:
Reaction formula (1) is as follows:
Figure C20051006077800071
In the formula (II), X is a halogen; E is hydrogen or halogen or cyano group;
In the formula (III), R 1, R 2Be group identical or inequality, hydrogen or C respectively do for oneself 1～C 6Alkyl or C 5～C 6Cyclic alkyl or benzyl or C 6～C 7Aryl; Perhaps R 1, R 2Become ring with N, R when becoming ring 1NR 2Represent Pyrrolidine base or hexahydropyridine base or morpholinyl or imidazolyl or connect triazolyl or 1,3,4-triazolyl.
What structural formula (II) was represented is many haloperidids of 2-phenolic compound.The compound of formula (II) representative all can have been bought from market, and is perhaps synthetic by known method.
What structural formula (III) was represented is aminated compounds, has both comprised secondary amine, also comprises primary amine.The compound of formula (II) representative all can have been bought from market.
Described acid binding agent comprises mineral alkali and organic bases, can be one of following: 1. yellow soda ash, 2. salt of wormwood, 3. sodium hydroxide, 4. potassium hydroxide, 5. pyridine, 6. N, N-lutidine, 7. triethylamine, 8. triethylene diamine.Preferred pyridine and salt of wormwood.
Described organic solvent can be selected according to different compounds (III), usually need be and (III) certain dissolubility is arranged all to (II), can be one of following: 1. N, dinethylformamide, 2. dimethyl sulfoxide (DMSO), 3. 1,4-dioxane.Be preferably 1, the 4-dioxane.As aminated compounds is gas, both can directly ventilate and carry out, and also can prepare solution in advance and use.
The temperature of reaction of described reaction is generally 50～150 ℃, is preferably 80～120 ℃, 100～120 ℃ of the bests.
The ratio of reactant formula (II) many halos 2-pyridol and formula (III) aminated compounds amount of substance is 1: 3.0 in the described reaction.The consumption of described organic solvent is: by the every throwing of formula (II) compound 1g 5～20mL with an organic solvent.
Described 6-substituted amido-3,5-dihalo-2-pyridol an alkali metal salt can be used for preparing O-(6-amido-2-pyridyl) thiophosphatephosphorothioate or phosphate derivative.Described O-(6-amido-2-pyridyl) thiophosphatephosphorothioate or phosphate derivative are a kind of novel agricultural insecticides, and aphid and mythimna separata are had special efficacy.
O-(6-amido-2-pyridyl) thiophosphatephosphorothioate or phosphate derivative structure are suc as formula shown in (I):
Figure C20051006077800081
In the formula (I), R 1, R 2Be group identical or inequality, hydrogen or C respectively do for oneself 1～C 6Alkyl or C 5～C 6Cyclic alkyl or benzyl or C 6-C 7Aryl; Perhaps R 1, R 2Become ring with N, R when becoming ring 1NR 2Represent Pyrrolidine base or hexahydropyridine base or morpholinyl or imidazolyl or connect triazolyl or 1,3,4-triazolyl;
R 3Be C 1～C 6Alkyl, Y represents C 1～C 6Alkoxyl group or C 1～C 6Alkylthio or R 4NR 5Base, wherein R 4, R 5Be identical or different groups, hydrogen or C respectively do for oneself 1～C 6Alkyl; X is a halogen; E is hydrogen or halogen or cyano group; Z is sulphur or oxygen.
The alkyl here is meant methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, n-hexyl; Aryl refers to phenyl, 4-chloro-phenyl-, 2,4 dichloro benzene base, 4-fluorophenyl, 4-aminomethyl phenyl and 4-trifluoromethyl; Halogen is meant F, Cl, Br and I.
Preferably, R 1, R 2Hydrogen or C respectively do for oneself 1～C 6Alkyl, perhaps R 1, R 2Become ring with N, R when becoming ring 1NR 2The amido of representative is a Pyrrolidine, imidazoles, and pyrazoles connects triazole, and 1,3,4-triazole, hexahydropyridine, morpholine, 1,4-Yi oxazine, perhaps R 1NR 2The amido of representative is a benzylamine, aniline, methylphenylamine, 4-chloroaniline, 2,4 dichloro aniline, 4-fluoroaniline, 4-monomethylaniline and 4-5-trifluoromethylaniline; Y is C 1～C 6Alkoxyl group; X is a chlorine; E is a hydrogen; Z is sulphur or oxygen.
Preferred, R 3For methyl or ethyl, Y are methoxy or ethoxy.R in the formula 1NR 2The group of representative is one of following: (1) dimethylin; (2) diethylin; (3) di-n-propylamine base; (4) diisopropylamino; (5) Di-n-Butyl Amine base; (6) first and second amidos; (7) first Propylamino; (8) methylamino; (9) ethylamino-; (10) Propylamino; (11) isopropylamine base; (12) n-butylamine-based; (13) isobutyl amine; (14) TERTIARY BUTYL AMINE base; (15) Pyrrolidine base; (16) hexahydropyridine base; (17) morpholinyl; (18) cyclopentamine base; (19) cyclohexylamino; (20) methylphenylamine base; (21) anilino.
Preferably, described derivative is one of following:
1. O, O-diethyl-O-(6-dimethylin-3,5-two chloro-2-pyridyl) thiophosphatephosphorothioate
2. O, O-diethyl-O-(6-diethylin-3,5-two chloro-2-pyridyl) thiophosphatephosphorothioate
3. O, O-diethyl-O-(6-di-n-propylamine base-3,5-two chloro-2-pyridyl) thiophosphatephosphorothioate
4. O, O-diethyl-O-(6-Pyrrolidine base-3,5-two chloro-2-pyridyl) thiophosphatephosphorothioate
5. O, O-diethyl-O-(6-hexahydropyridine base-3,5-two chloro-2-pyridyl) thiophosphatephosphorothioate
6. O, O-diethyl-O-(6-morpholinyl-3,5-two chloro-2-pyridyl) thiophosphatephosphorothioate
7. O, O-dimethyl-O-(6-dimethylin-3,5-two chloro-2-pyridyl) thiophosphatephosphorothioate
8. O, O-dimethyl-O-(6-diethylin-3,5-two chloro-2-pyridyl) thiophosphatephosphorothioate
9. O, O-diethyl-O-(6-dimethylin-3,5-two chloro-2-pyridyl) phosphoric acid ester
10. O, O-diethyl-O-(6-diethylin-3,5-two chloro-2-pyridyl) phosphoric acid ester
Described O-(6-amido-2-pyridyl) thiophosphatephosphorothioate or phosphate derivative can be by intermediate formula (IV) 6-substituted amidos-3,5-dihalo-2-pyridol an alkali metal salt and phosphoric acid ester muriate or thiophosphatephosphorothioate muriate shown in formula V, under the phase-transfer catalyst effect, in organic solvent, react, promptly get the O-shown in the described formula (I) (6-amido-2-pyridyl) thiophosphatephosphorothioate or phosphate derivative, described organic solvent is one of following: 1. benzene, 2. toluene, 3. chlorobenzene, 4. methylene dichloride;
What the structure formula V was represented is phosphoric acid ester or thiophosphatephosphorothioate muriate, and the compound of formula V representative all can have been bought from market, perhaps synthetic by known method.
Reaction formula (2) is as follows:
Figure C20051006077800101
Described phase-transfer catalyst is one of following: 1. 4-dimethylamino pyridine, 2. triethylene diamine, 3. triethylamine, 4. N, accelerine, 5. triethyl benzyl ammonia chloride, 6. trimethyl benzyl ammonia chloride; The consumption of described phase-transfer catalyst is 0.1～0.5% of reaction raw materials formula (IV) compound mole number.
Described organic solvent is toluene or methylene dichloride.
The amount of substance ratio is 1: 1.0～1.5 in described formula (IV) compound and phosphoric acid ester muriate shown in formula V or the reaction of thiophosphatephosphorothioate muriate, and the consumption of described organic solvent is: by the every throwing of formula (IV) compound 1g 1～5mL with an organic solvent.
6-substituted amido-3 of the present invention, the beneficial effect of 5-dihalo-2-pyridol an alkali metal salt is mainly reflected in: by 6-substituted amido-3,5-dihalo-2-pyridol an alkali metal salt prepares gained O-(6-amido-2-pyridyl) thiophosphatephosphorothioate or phosphate derivative has excellent insecticidal activity, especially aphid, mythimna separata had good effect, and low toxicity, environmentally friendly, do not injure crop, have great DEVELOPMENT PROSPECT.
(4) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Part is as shown in table 1 by (IV) obtained compound (I):
Figure C20051006077800111
Table 1
Compound number R 1NHR 2 R 3 Y X E Z B
1 CH 3NHCH 3 C 2H 5 OC 2H 5 Cl H S Na
2 C 2H 5NHC 2H 5 C 2H 5 OC 2H 5 Cl H S Na
3 n-C 3H 7NHn-C 3H 7 C 2H 5 OC 2H 5 Cl H S Na
4 n-C 4H 9NHn-C 4H 9 C 2H 5 OC 2H 5 Cl H S Na
5 CH 3NHC 2H 5 C 2H 5 OC 2H 5 Cl H S Na
6 CH 3NHn-C 3H 7 C 2H 5 OC 2H 5 Cl H S Na
7 Pyrrolidine C 2H 5 OC 2H 5 Cl H S Na
8 Hexahydropyridine C 2H 5 OC 2H 5 Cl H S Na
9 Morpholine C 2H 5 OC 2H 5 Cl H S Na
10 CH 3NH 2 C 2H 5 OC 2H 5 Cl H S Na
11 C 2H 5NH 2 C 2H 5 OC 2H 5 Cl H S Na
12 n-C 3H 7NH 2 C 2H 5 OC 2H 5 Cl H S Na
13 iso-C 3H 7NH 2 C 2H 5 OC 2H 5 Cl H S Na
14 Hexahydroaniline C 2H 5 OC 2H 5 Cl H S Na
15 PhCH 2NH 2 C 2H 5 OC 2H 5 Cl H S Na
16 PhNH 2 C 2H 5 OC 2H 5 Cl H S Na
17 CH 3NHCH 3 CH 3 OCH 3 Cl H S Na
18 C 2H 5NHC 2H 5 CH 3 OCH 3 Cl H S K
19 n-C 3H 7NHn-C 3H 7 CH 3 OCH 3 Cl H S K
20 CH 3NHC 2H 5 CH 3 OCH 3 Cl H S K
21 CH 3NHn-C 3H 7 CH 3 OCH 3 Cl H S K
22 CH 3NH 2 CH 3 OCH 3 Cl H S K
23 C 2H 5NH 2 CH 3 OCH 3 Cl H S K
24 n-C 3H 7NH 2 CH3 OCH 3 Cl H S K
25 iso-C 3H 7NH 2 CH 3 OCH 3 Cl H S K
26 CH 3NHCH 3 C 2H 5 OC 2H 5 Cl H O Na
27 C 2H 5NHC 2H 5 C 2H 5 OC 2H 5 Cl H O Na
28 CH 3NH 2 C 2H 5 OC 2H 5 Cl H O Na
29 C 2H 5NH 2 C 2H 5 OC 2H 5 Cl H O Na
30 CH 3NHCH 3 CH 3 OCH 3 Cl H O Na
31 C 2H 5NHC 2H 5 CH 3 OCH 3 Cl H O Na
32 CH 3NHCH 3 C 2H 5 SCH 3 Cl H S Na
33 CH 3NHCH 3 C 2H 5 CH 3NCH 3 Cl H S K
34 C 2H 5NHC 2H 5 C 2H 5 CH 3NCH 3 Br H O K
35 C 2H 5NHC 2H 5 C 2H 5 CH 3NCH 3 Cl Cl S K
36 CH 3NHCH 3 C 2H 5 CH 3NCH 3 Cl Cl O K
37 C 2H 5NHC 2H 5 C 2H 5 C 2H 5NC 2H 5 Br Br S K
38 CH 3NHCH 3 C 2H 5 n-C 3H 7Nn-C 3H 7 Br Br O K
39 C 2H 5NHC 2H 5 C 2H 5 CH 3NCH 3 Cl CN S K
40 CH 3NHCH 3 C 2H 5 CH 3NCH 3 Cl CN O K
41 C 2H 5NHC 2H 5 C 2H 5 C 2H 5NC 2H 5 Br CN O K
Because it is more to the present invention relates to material, but the preparation method is identical substantially, the replacement of just relevant group is described in detail its preparation so locate only to choose wherein several representative species:
Embodiment 1:O, O-diethyl-O-(6-dimethylin-3,5-two fluoro-2-pyridyl) thiophosphatephosphorothioate (compound 1)
In the 250mL there-necked flask, add 3,5,6-phenolate trichloropyridine (9.9g, 50.0mmol), 1,4-dioxane (150mL), pyridine (3.95g, 50.0mmol), stirring and dissolving slowly is warming up to 100～120 ℃, slowly feeds dimethylamine gas simultaneously, insulation reaction 24 hours, be cooled to below 50 ℃, filter out the pyridine hydrochloride that reaction generates earlier, dried solvent is taken off in underpressure distillation, slowly drip 30%NaOH and carry out alkaline hydrolysis in resistates, controlled temperature is at 0～25 ℃.Alkaline hydrolysis finishes after-filtration, 6-dimethylin-3,5-dichloropyridine sodium phenolate product (content the is 63%) 15.3g that wets, yield 84%.
Get top made 6-dimethylin-3, the 5-dichloropyridine sodium phenolate product 9.1g (25mmol) that wets adds 15mL water, 10mL CH in reactor 2Cl 2, 0.25g polyoxyethylene glycol PG26-2, the 0.006g triethyl benzyl ammonia chloride, 2.2g NaCl, 0.3g NaOH stirring to pulp under room temperature condition slowly splashes into O, and O-o,o-diethylthiophosphoryl chloride 4.9g (26.3mmol) refluxed 3 hours in 40 ℃.Cooling, static layering, get oil reservoir, under reduced pressure solvent evaporated gets O, O-diethyl-O-(6-dimethylin-3,5-two chloro-2-pyridyl) thiophosphatephosphorothioate crude product is further used column chromatography (silica gel, eluent: sherwood oil/methylene dichloride=3/1, volume ratio) purify pure product 7.6g, yield 84.6%.
Compound 1 characterizes: 1H MR (CDCl 3, 400MHz) δ: 1.41 (t, 6H, J=7.2Hz), 3.03 (s, 6H), 4.36 (dq, 4H, J H-H=7.2Hz, 3J P-H=9.6Hz), 7.57 (s, 1H). 31P NMR (CDCl 3, 162MHz) δ: 60.98.MS (70eV) m/z:358 (M +).
Embodiment 2:O, O-diethyl-O-(6-diethylin-3,5-two chloro-2-pyridyl) thiophosphatephosphorothioate (compound 2)
In the 250mL there-necked flask, add 3,5,6-phenolate trichloropyridine (9.9g, 50.0mmol), 1,4-dioxane (150mL), pyridine (3.95g, 50.0mmol), stirring and dissolving slowly is warming up to 100～120 ℃, slowly drips diethylamine (11g simultaneously, 150mmol), insulation reaction 28 hours is cooled to below 50 ℃, filter out the pyridine hydrochloride that reaction generates earlier, dried solvent is taken off in underpressure distillation, slowly drips 30%NaOH and carry out alkaline hydrolysis in resistates, and controlled temperature is at 0～25 ℃.Alkaline hydrolysis finishes after-filtration, 6-diethylin-3,5-dichloropyridine sodium phenolate product (content the is 60%) 17.3g that wets, yield 80.7%.
Get top made 6-diethylin-3, the 5-dichloropyridine sodium phenolate product 10.7g (25mmol) that wets adds 15mL water, 10mL CH in reactor 2Cl 2, 0.25g polyoxyethylene glycol PG26-2, the 0.006g triethyl benzyl ammonia chloride, 2.2g NaCl, 0.3g NaOH stirring to pulp under room temperature condition slowly splashes into O, and O-o,o-diethylthiophosphoryl chloride 4.9g (26.3mmol) refluxed 3 hours in 40 ℃.Cooling, static layering, get oil reservoir, under reduced pressure solvent evaporated gets O, O-diethyl-O-(6-diethylin-3,5-two chloro-2-pyridyl) thiophosphatephosphorothioate crude product is further used column chromatography (silica gel, eluent: sherwood oil/methylene dichloride=3/1, volume ratio) purify pure product 7.8g, yield 80.6%.
Compound 2 characterizes: 1H NMR (CDCl 3, 400MHz) δ: 1.19 (t, 6H, J=7.2Hz), 1.40 (t, 6H, J=7.0Hz), 3.45 (q, 4H, J=7.2Hz), 4.34 (dq, 4H, J H-H=7.0Hz, 3J P-H=9.6Hz), 7.55 (s, 1H). 31P NMR (CDCl 3, 162MHz) δ: 60.92.MS (70eV) m/z:386 (M +).
Embodiment 3:O, O-diethyl-O-(6-di-n-propylamine base-3,5-two chloro-2-pyridyl) thiophosphatephosphorothioate (compound 3)
In the 250mL there-necked flask, add 3,5,6-phenolate trichloropyridine (9.9g, 50.0mmol), 1,4-dioxane (150mL), pyridine (3.95g, 50.0mmol), stirring and dissolving slowly is warming up to 100～120 ℃, slowly drips di-n-propylamine (15g simultaneously, 150mmol), insulation reaction 31 hours is cooled to below 50 ℃, filter out the pyridine hydrochloride that reaction generates earlier, dried solvent is taken off in underpressure distillation, slowly drips 30%NaOH and carry out alkaline hydrolysis in resistates, and controlled temperature is at 0～25 ℃.Alkaline hydrolysis finishes after-filtration, 6-di-n-propylamine base-3,5-dichloropyridine sodium phenolate product (content the is 62%) 17.9g that wets, yield 77.9%.
Get top made 6-diethylin-3, the 5-dichloropyridine sodium phenolate product 11.5g (25mmol) that wets adds 15mL water, 13mL CH in reactor 2Cl 2, 0.25g polyoxyethylene glycol PG26-2, the 0.006g triethyl benzyl ammonia chloride, 2.2g NaCl, 0.3g NaOH stirring to pulp under room temperature condition slowly splashes into O, and O-o,o-diethylthiophosphoryl chloride 4.9g (26.5mmol) refluxed 3 hours in 40 ℃.Cooling, static layering, get oil reservoir, under reduced pressure solvent evaporated gets O, O-diethyl-O-(6-di-n-propylamine base-3,5-two chloro-2-pyridyl) thiophosphatephosphorothioate crude product is further used column chromatography (silica gel, eluent: sherwood oil/methylene dichloride=3/1, volume ratio) purify pure product 8.1g, yield 78.1%.
Compound 3 characterizes: 1H NMR (CDCl 3, 400MHz) δ: 0.88 (t, 6H, J=7.6Hz), 1.40 (t, 6H, J=6.8Hz), 1.62 (m, 4H), 3.35 (t, 4H, J=7.6Hz), 4.32 (dq, 4H, J H-H=6.8Hz, 3J P-H=9.6Hz), 7.54 (s, 1H). 31P NMR (CDCl 3, 162MHz) δ: 60.82.MS (70eV) m/z:414 (M +).
Embodiment 4:O, O-diethyl-O-(6-Pyrrolidine base-3,5-two chloro-2-pyridyl) thiophosphatephosphorothioate (compound 7)
In the 250mL there-necked flask, add 3,5,6-phenolate trichloropyridine (9.9g, 50.0mmol), 1,4-dioxane (150mL), pyridine (3.95g, 50.0mmol), stirring and dissolving slowly is warming up to 100～120 ℃, slowly drips Pyrrolidine (10.7g simultaneously, 150mmol), insulation reaction 25 hours is cooled to below 50 ℃, filter out the pyridine hydrochloride that reaction generates earlier, dried solvent is taken off in underpressure distillation, slowly drips 30%NaOH and carry out alkaline hydrolysis in resistates, and controlled temperature is at 0～25 ℃.Alkaline hydrolysis finishes after-filtration, 6-Pyrrolidine base-3,5-dichloropyridine sodium phenolate product (content the is 65%) 15.3g that wets, yield 78%.
Get top made 6-Pyrrolidine base-3, the 5-dichloropyridine sodium phenolate product 9.8g (25mmol) that wets adds 15mL water, 13mL CH in reactor 2Cl 2, 0.25g polyoxyethylene glycol PG26-2, the 0.006g triethyl benzyl ammonia chloride, 2.2g NaCl, 0.3g NaOH stirring to pulp under room temperature condition slowly splashes into O, and O-o,o-diethylthiophosphoryl chloride 4.9g (26.3mmol) refluxed 3 hours in 40 ℃.Cooling, static layering, get oil reservoir, under reduced pressure solvent evaporated gets O, O-diethyl-O-(6-Pyrrolidine base-3,5-two chloro-2-pyridyl) thiophosphatephosphorothioate crude product is further used column chromatography (silica gel, eluent: sherwood oil/methylene dichloride=3/2, volume ratio) purify pure product 7.3g, yield 75%.
Embodiment 5:O, O-diethyl-O-(6-hexahydropyridine base-3,5-two chloro-2-pyridyl) thiophosphatephosphorothioate (compound 8)
In the 250mL there-necked flask, add 3,5,6-phenolate trichloropyridine (9.9g, 50.0mmol), 1,4-dioxane (150mL), pyridine (3.95g, 50.0mmol), stirring and dissolving slowly is warming up to 100～120 ℃, slowly drips hexahydropyridine (12.6g simultaneously, 150mmol), insulation reaction 25 hours is cooled to below 50 ℃, filter out the pyridine hydrochloride that reaction generates earlier, dried solvent is taken off in underpressure distillation, slowly drips 30%NaOH and carry out alkaline hydrolysis in resistates, and controlled temperature is at 0～25 ℃.Alkaline hydrolysis finishes after-filtration, 6-hexahydropyridine base-3,5-dichloropyridine sodium phenolate product (content the is 60%) 17.7g that wets, yield 79.1%.
Get top made 6-hexahydropyridine base-3, the 5-dichloropyridine sodium phenolate product 11.2g (25mmol) that wets adds 15mL water, 12mLCH in reactor 2Cl 2, 0.25g polyoxyethylene glycol PG26-2, the 0.006g triethyl benzyl ammonia chloride, 2.2g NaCl, 0.3g NaOH stirring to pulp under room temperature condition slowly splashes into O, and O-o,o-diethylthiophosphoryl chloride 4.9g (26.3mmol) refluxed 3 hours in 40 ℃.Cooling, static layering, get oil reservoir, under reduced pressure solvent evaporated gets O, O-diethyl-O-(6-hexahydropyridine base-3,5-two chloro-2-pyridyl) thiophosphatephosphorothioate crude product is further used column chromatography (silica gel, eluent: sherwood oil/methylene dichloride=3/2, volume ratio) purify pure product 7.4g, yield 74.2%.
Compound 8 characterizes: 1H NMR (CDCl 3, 400MHz) δ: 1.46 (t, 6H, J=6.8Hz), 1.60-1.80 (m, 6H), 3.38 (t, 4H, J=5.6Hz), 4.33-4.47 (m, 4H), 7.65 (s, 1H). 31PNMR (CDCl 3, 162MHz) δ: 61.10.MS (70eV) m/z:398 (M +).
Embodiment 6:O, O-diethyl-O-(6-morpholinyl-3,5-two chloro-2-pyridyl) thiophosphatephosphorothioate (compound 9)
In the 250mL there-necked flask, add 3,5,6-phenolate trichloropyridine (9.9g, 50.0mmol), 1,4-dioxane (150mL), pyridine (3.95g, 50.0mmol), stirring and dissolving slowly is warming up to 100～120 ℃, slowly drips morpholine (13.1g simultaneously, 150mmol), insulation reaction 25 hours is cooled to below 50 ℃, filter out the pyridine hydrochloride that reaction generates earlier, dried solvent is taken off in underpressure distillation, slowly drips 30%NaOH and carry out alkaline hydrolysis in resistates, and controlled temperature is at 0～25 ℃.Alkaline hydrolysis finishes after-filtration, 6-morpholinyl-3,5-dichloropyridine sodium phenolate product (content the is 63%) 17.6g that wets, yield 81.8%.
Get top made 6-morpholinyl-3, the 5-dichloropyridine sodium phenolate product 10.8g (25mmol) that wets adds 15mL water, 13mL CH in reactor 2Cl 2, 0.25g polyoxyethylene glycol PG26-2, the 0.006g triethyl benzyl ammonia chloride, 2.2g NaCl, 0.3g NaOH stirring to pulp under room temperature condition slowly splashes into O, and O-o,o-diethylthiophosphoryl chloride 4.9g (26.3mmol) refluxed 3 hours in 40 ℃.Cooling, static layering, get oil reservoir, under reduced pressure solvent evaporated gets O, O-diethyl-O-(6-morpholinyl-3,5-two chloro-2-pyridyl) thiophosphatephosphorothioate crude product is further used column chromatography (silica gel, eluent: sherwood oil/methylene dichloride=3/2, volume ratio) purify pure product 7.9g, yield 78.8%.
Compound 9 characterizes: 1H NMR (CDCl 3, 400MHz) δ: 1.41 (t, 6H, J=7.2Hz), 3.41 (t, 4H, J=5.2Hz), 3.82 (t, 4H, J=5.2Hz), 4.35 (dq, 4H, J H-H=7.0Hz, 3J P-H=9.6Hz), 7.65 (s, 1H). 31P NMR (CDCl 3, 162MHz) δ: 60.85.MS (70eV) m/z:400 (M +)
Embodiment 7:O, O-dimethyl-O-(6-dimethylin-3,5-two chloro-2-pyridyl) thiophosphatephosphorothioate (compound 17)
Get by the obtained 6-dimethylin-3 of embodiment 1 method, 5-dichloropyridine sodium phenolate wets, and (content 63% 50mmol), adds 30mL water, 20mL CH to product 18.2g in reactor 2Cl 2, 0.5g polyoxyethylene glycol PG26-2, the 0.012g triethyl benzyl ammonia chloride, 4.4g NaCl, 0.6g NaOH stirring to pulp under room temperature condition slowly splashes into O, and O-dimethyl thiophosphoryl chloride 8.4g (52.5mmol) refluxed 3 hours in 40 ℃.Cooling, static layering, get oil reservoir, under reduced pressure solvent evaporated gets O, O-dimethyl-O-(6-dimethylin-3,5-two chloro-2-pyridyl) thiophosphatephosphorothioate crude product is further used column chromatography (silica gel, eluent: sherwood oil/methylene dichloride=3/1, volume ratio) purify pure product 13.1g, yield 79.2%.
Embodiment 8:O, O-diethyl-O-(6-dimethylin-3,5-two chloro-2-pyridyl) phosphoric acid ester (compound 26)
Get by the obtained 6-dimethylin-3 of embodiment 1 method, 5-dichloropyridine sodium phenolate wets, and (content 63% 50mmol), adds 30mL water, 20mL CH to product 18.2g in reactor 2Cl 2, 0.5g polyoxyethylene glycol PG26-2, the 0.012g triethyl benzyl ammonia chloride, 4.4g NaCl, 0.6g NaOH stirring to pulp under room temperature condition slowly splashes into O, and O-diethylchlorophosphate (C2H5O)2P(O)Cl 9.1g (52.5mmol) refluxed 3 hours in 40 ℃.Cooling, static layering, get oil reservoir, under reduced pressure solvent evaporated gets O, O-diethyl-O-(6-dimethylin-3,5-two chloro-2-pyridyl) sulfuric ester crude product is further used column chromatography (silica gel, eluent: sherwood oil/methylene dichloride=3/1, volume ratio) purify pure product 13.0g, yield 75.8%.
Embodiment 9:S-methyl-O-ethyl-O-(6-dimethylin-3,5-two chloro-2-pyridyl) phosphorodithioate (compound 32)
Get by the obtained 6-dimethylin-3 of embodiment 1 method, 5-dichloropyridine sodium phenolate wets, and (content 63% 50mmol), adds 30mL water, 30mL CH to product 18.2g in reactor 2Cl 2, 0.5g polyoxyethylene glycol PG26-2, the 0.012g triethyl benzyl ammonia chloride, 4.4g NaCl, 0.6g NaOH stirring to pulp under room temperature condition slowly splashes into S-methyl-O-diethyldithioposphoric acid ester muriate 9.9g (52.5mmol), refluxes 3 hours in 40 ℃.Cooling, static layering, get oil reservoir, under reduced pressure solvent evaporated gets S-methyl-O-ethyl-O-(6-dimethylin-3,5-two chloro-2-pyridyl) phosphorodithioate crude product, further use column chromatography (silica gel, eluent: sherwood oil/methylene dichloride=3/2, volume ratio) purify pure product 12.3g, yield 74.5%.
Embodiment 10:N, N-dimethyl-O-ethyl-O-(6-diethylin-3,4,5-trichloro-2-pyridyl) thio-phosphamide (compound 35)
In the 250mL there-necked flask, add 3,4,5,6-4 chloro pyridine phenol (11.7g, 50.0mmol), 1,4-dioxane (150mL), pyridine (3.95g, 50.0mmol), stirring and dissolving slowly is warming up to 100～120 ℃, slowly drip simultaneously diethylamine (11g, 150mmol), insulation reaction 30 hours, be cooled to below 50 ℃, filter out the pyridine hydrochloride that reaction generates earlier, dried solvent is taken off in underpressure distillation, slowly drip 30%KOH and carry out alkaline hydrolysis in resistates, controlled temperature is at 0～25 ℃.Alkaline hydrolysis finishes after-filtration, 6-diethylin-3,4,5-phenolate trichloropyridine sylvite product (content the is 61%) 20.6g that wets, yield 81.7%.
Get top made 6-diethylin-3,4, the 5-phenolate trichloropyridine sylvite product 11.9g (25mmol) that wets adds 15mL water, 15mL CH in reactor 2Cl 2, 5g polyoxyethylene glycol PG26-2, the 0.006g triethyl benzyl ammonia chloride, 2.2g NaCl, 0.3gNaOH is stirring to pulp under room temperature condition, slowly splashes into N, and N-dimethyl-O-ethylenebis dithiocarbamate phosphamide muriate 4.9g (26.3mm0l) refluxed 3 hours in 40 ℃.Cooling, static layering is got oil reservoir, under reduced pressure solvent evaporated, get N, N-dimethyl-O-ethyl-O-(6-diethylin-3,4,5-trichloro-2-pyridyl) thio-phosphamide crude product, further use column chromatography (silica gel, eluent: sherwood oil/methylene dichloride=3/2, volume ratio) purify pure product 8.5g, yield 80.8%.
Embodiment 11:N, N-dimethyl-O-ethyl-O-(6-dimethylin-3,4,5-trichloro-2-pyridyl) phosphamide (compound 36)
In the 250mL there-necked flask, add 3,4,5,6-4 chloro pyridine phenol (11.7g, 50.0mmol), 1,4-dioxane (150mL), pyridine (3.95g, 50.0mmol), stirring and dissolving slowly is warming up to 100～120 ℃, simultaneously slowly feed dimethylamine gas, insulation reaction 30 hours is cooled to below 50 ℃, filter out the pyridine hydrochloride that reaction generates earlier, dried solvent is taken off in underpressure distillation, slowly drips 30%KOH and carry out alkaline hydrolysis in resistates, and controlled temperature is at 0～25 ℃.Alkaline hydrolysis finishes after-filtration, 6-dimethylin-3,4,5-phenolate trichloropyridine sylvite product (content the is 63%) 18.3g that wets, yield 82.4%.
Get top made 6-dimethylin-3,4, the 5-phenolate trichloropyridine sylvite product 11.1g (25mmol) that wets adds 15mL water, 15mL CH in reactor 2Cl 2, 0.25g polyoxyethylene glycol PG26-2, the 0.006g triethyl benzyl ammonia chloride, 2.2g NaCl, 0.3g NaOH stirring to pulp under room temperature condition slowly splashes into N, and N-dimethyl-O-ethyl phosphamide muriate 4.5g (26.3mmol) refluxed 3 hours in 40 ℃.Cooling, static layering is got oil reservoir, under reduced pressure solvent evaporated, get N, N-dimethyl-O-ethyl-O-(6-dimethylin-3,4,5-trichloro-2-pyridyl) phosphamide crude product, further use column chromatography (silica gel, eluent: sherwood oil/methylene dichloride=3/2, volume ratio) purify pure product 7.6g, yield 80.9%.
Embodiment 12:N, N-dimethyl-O-ethyl-O-(6-dimethylin-3,5-two chloro-4-cyano group-2-pyridyl) phosphamide (compound 40)
In the 250mL there-necked flask, add 3,5,6-three chloro-4-cyanopyridine phenol (11.7g, 50.0mmol), 1,4-dioxane (150mL), pyridine (3.95g, 50.0mmol), stirring and dissolving slowly is warming up to 100～120 ℃, slowly feeds dimethylamine gas simultaneously, insulation reaction 30 hours, be cooled to below 50 ℃, filter out the pyridine hydrochloride that reaction generates earlier, dried solvent is taken off in underpressure distillation, slowly drip 30%NaOH and carry out alkaline hydrolysis in resistates, controlled temperature is at 0～25 ℃.Alkaline hydrolysis finishes after-filtration, 6-dimethylin-3,5-two chloro-4-cyanopyridine sodium phenolates product (content the is 59%) 18.4g that wets, yield 80.4%.
Get top made 6-dimethylin-3, the 5-two chloro-4-cyanopyridine phenol sylvite product 11.4g (25mmol) that wets adds 15mL water, 15mL CH in reactor 2Cl 2, 0.25g polyoxyethylene glycol PG26-2, the 0.006g triethyl benzyl ammonia chloride, 2.2g NaCl, 0.3g NaOH stirring to pulp under room temperature condition slowly splashes into N, and N-dimethyl-O-ethyl phosphamide muriate 4.5g (26.3mmol) refluxed 3 hours in 40 ℃.Cooling, static layering, get oil reservoir, under reduced pressure solvent evaporated gets N, N-dimethyl-O-ethyl-O-(6-dimethylin-3,5-two chloro-4-cyano group-2-pyridyl) phosphamide crude product is further used column chromatography (silica gel, eluent: sherwood oil/methylene dichloride=3/2, volume ratio) purify pure product 7.0g, yield 78.7%.
Embodiment 13: insecticidal activity assay
(1) the active mensuration of killing aphis
Test materials: aphis craccivora (Aphis meolicaginis Koch) is indoor to be raised for many years
Crop: broad bean tender shoots
Method: pickling process, the one-tenth aphid of indoor feeding is connected on the previously prepd Semen Viciae fabae bud, treat that aphid is after fixing on the bean seedlings, bean seedlings are immersed soup with aphid, insert then on the sponge of preserving moisture, cover upper glass cover, put 23 ℃ of left and right sides thermostatic chambers, check result after 24 hours.
Method of calculation: mortality ratio (%)=[dead borer population/total borer population] * 100
(2) kill the active mensuration of mythimna separata
Test materials: mythimna separata (Leucania seoarata Walker) is indoor to be raised for many years
Crop: maize seedling
Method: pickling process, the maize seedling of previously prepd 3～5 leaves is cut the immersion soup, take out airing then after, its maize seedling cut into the finger line pipe puts into 3 instar larvaes again.Put 25 ℃ of left and right sides thermostatic chambers, check result after 24 hours or 48 hours.
Method of calculation: mortality ratio (%)=[dead borer population/total borer population] * 100
Statistics sees Table 2:
Table 2: the killing aphis of part of compounds, kill the mythimna separata activity
Compound number Active material concentration (mg/L) Aphid mortality ratio % Mythimna separata mortality ratio %
1 100 100 100
2 125 100 100
3 500 99.6 96.3
7 500 100 95.8
8 500 100 98.3
9 500 97.5 95.2
13 200 100 100
17 100 98.7 96.6
18 100 97.2 93.5
32 500 100 100
35 500 99.4 99.6
36 500 100 100
40 500 98.3 99.2

Claims (9)

1. 6-substituted amido-3,5-dihalo-2-pyridol an alkali metal salt, structure is suc as formula shown in (IV):
Figure C2005100607780002C1
In the formula (IV), R 1, R 2Be group identical or inequality, C respectively does for oneself 1～C 6Alkyl; Perhaps R 1, R 2Become ring with N, R when becoming ring 1NR 2Represent Pyrrolidine base or hexahydropyridine base or morpholinyl; X is a halogen; E is a hydrogen; B is potassium or sodium.
2. the described 6-substituted amido-3 of claim 1,5-dihalo-2-pyridol an alkali metal salt is characterized in that R 1, R 2C respectively does for oneself 1～C 3Alkyl, perhaps R 1, R 2Become ring with N, R when becoming ring 1NR 2The amido of representative is the Pyrrolidine base, hexahydropyridine base, or morpholinyl; X is a chlorine; E is a hydrogen; B is a sodium.
3. prepare 6-substituted amido-3 as claimed in claim 1, the method of 5-dihalo-2-pyridol an alkali metal salt, it is characterized in that described 6-substituted amido-3,5-dihalo-2-pyridol an alkali metal salt makes as follows: by the many halo 2-pyridol of structural formula shown in (II) with suc as formula the aminated compounds shown in (III) with 1: 1～10 amount of substance ratio, at the same time in the organic solvent of dissolution type (II) and formula (III), acid binding agent exists down, in room temperature to solvent boiling point temperature range internal reaction 5～40 hours, the gained reactant is handled suc as formula the 6-substituted amido-3 shown in (IV) through NaOH or KOH, 5-dihalo-2-pyridol an alkali metal salt;
Figure C2005100607780003C1
In the formula (II), X is a halogen; E is a hydrogen;
In the formula (III), R 1, R 2Be group identical or inequality, C respectively does for oneself 1～C 6Alkyl; Perhaps R 1, R 2Become ring with N, R when becoming ring 1NR 2Represent Pyrrolidine base or hexahydropyridine base or morpholinyl.
4. 6-substituted amido-3 as claimed in claim 3, the preparation method of 5-dihalo-2-pyridol an alkali metal salt is characterized in that described acid binding agent is one of following:
1. yellow soda ash, 2. salt of wormwood, 3. sodium hydroxide, 4. potassium hydroxide, 5. pyridine, 6. triethylamine, 7. triethylene diamine.
5. 6-substituted amido-3 as claimed in claim 4, the preparation method of 5-dihalo-2-pyridol an alkali metal salt is characterized in that described organic solvent is one of following: 1. N, dinethylformamide, 2. dimethyl sulfoxide (DMSO), 3. 1,4-dioxane.
6. 6-substituted amido-3 as claimed in claim 5, the preparation method of 5-dihalo-2-pyridol an alkali metal salt is characterized in that described organic solvent is 1, the 4-dioxane.
7. 6-substituted amido-3 as claimed in claim 3, the preparation method of 5-dihalo-2-pyridol an alkali metal salt is characterized in that temperature of reaction is 80～120 ℃.
8. 6-substituted amido-3 as claimed in claim 3, the preparation method of 5-dihalo-2-pyridol an alkali metal salt, the ratio that it is characterized in that reactant formula (II) many halos 2-pyridol and formula (III) aminated compounds amount of substance is 1: 3.0, and the consumption of described organic solvent is: by the every throwing of formula (II) compound 1g 5～20mL with an organic solvent.
9. 6-substituted amido-3 as claimed in claim 1,5-dihalo-2-pyridol an alkali metal salt are used for preparing the purposes of O-(6-amido-2-pyridyl) thiophosphatephosphorothioate.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4016225A (en) * 1973-05-21 1977-04-05 The Dow Chemical Company Process for preparing phosphorothioates and phenylphosphonothioates
US4489068A (en) * 1983-04-28 1984-12-18 The Dow Chemical Company Method and composition for enhancing the insecticidal activity of certain organophosphorus compounds
EP0185282A2 (en) * 1984-12-18 1986-06-25 Bayer Ag Pyridyl-thionophosphoric acid esters
EP0199060A2 (en) * 1985-04-03 1986-10-29 Shell Agrar GmbH & Co. KG Pyridyl phosphoric-acid esters
US4777164A (en) * 1983-04-28 1988-10-11 The Dow Chemical Company Method and composition for enhancing the insecticidal activity of certain organophosphorus compounds
US5075294A (en) * 1987-10-14 1991-12-24 Hoechst Aktiengesellschaft Pyridyl phosphates, compositions containing them and their use as pesticides

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4016225A (en) * 1973-05-21 1977-04-05 The Dow Chemical Company Process for preparing phosphorothioates and phenylphosphonothioates
US4489068A (en) * 1983-04-28 1984-12-18 The Dow Chemical Company Method and composition for enhancing the insecticidal activity of certain organophosphorus compounds
US4777164A (en) * 1983-04-28 1988-10-11 The Dow Chemical Company Method and composition for enhancing the insecticidal activity of certain organophosphorus compounds
EP0185282A2 (en) * 1984-12-18 1986-06-25 Bayer Ag Pyridyl-thionophosphoric acid esters
EP0199060A2 (en) * 1985-04-03 1986-10-29 Shell Agrar GmbH & Co. KG Pyridyl phosphoric-acid esters
US5075294A (en) * 1987-10-14 1991-12-24 Hoechst Aktiengesellschaft Pyridyl phosphates, compositions containing them and their use as pesticides

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