CN1094127C - Substituted picolyl phosphoric acid easter with insecticidal activity and its prepn. method - Google Patents
Substituted picolyl phosphoric acid easter with insecticidal activity and its prepn. method Download PDFInfo
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- CN1094127C CN1094127C CN97109262A CN97109262A CN1094127C CN 1094127 C CN1094127 C CN 1094127C CN 97109262 A CN97109262 A CN 97109262A CN 97109262 A CN97109262 A CN 97109262A CN 1094127 C CN1094127 C CN 1094127C
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Abstract
The present invention relates to a substituted picolyl phosphoric acid easter with insecticidal activity and preparation method thereof, which belongs to the technical field of fine organic synthesis. A general formula as shown in the right formula is substituted picolyl phosphoric acid easter with insecticidal activity, R<1> and R<2> in the general formula represent alkyl, phenyl and substituted phenyl which are halogen, nitro and methyl from C1 to C5, R<1> and R<2> are the same or different, X represents O or S, Z represents S or NH, and Y represents H or Cl. The compound has obvious activity for killing aphids or red spiders, and can be used as a pesticide or an acaricide.
Description
The present invention relates to substituted picolyl phosphoric acid easter compound that has insecticidal activity and preparation method thereof, and it the invention belongs to Minute Organic Synthesis as sterilant, acaricidal biological activity.
A class of Fa Xianing is called the sterilant of " anabasine " in recent ten years, as Imidacloprid [JP02,207,083 (1990)], Ac-etamiprid[JP05,155,722 (1993)] and Nitenpyan[EP392,560 (1990)] common characteristic is arranged, promptly all contain 6-chloro-3-picolyl, the present invention is incorporated into preparation substituted picolyl phosphoric acid easter compound in the phosphorated structure with 6-chloro-3-picolyl.
The objective of the invention is to explore insecticidal activity compound preferably, provide a class to have insecticidal activity and with the new type of phosphate analog derivative and the synthetic method of acaricidal activity.
The present invention proposes class new type of phosphate analog derivative a---substituted picolyl phosphoric acid easter, its general structure following (I)
R in the formula
1, R
2Expression C
1～C
5Alkyl, phenyl or substituted-phenyl, substituting group is halogen, nitro, methyl
R
1With R
2Identical or inequality
X represents O or S
Z represents S or NH
Y represents H or Cl
The compound that belongs to formula of the present invention (I) comprises with the represented substituted pyridines methyl phosphoramidate of following general formula I-1; Substituted pyridines thiomethyl thiolophosphate with general formula I-2 expression.
R in the formula
1, R
2, in X, Y and the formula (I) definition identical
The compound of above-mentioned formula provided by the invention (I) has insects and mite class kills activity significantly, thereby can be used as the effective ingredient and the acaricidal effective ingredient of sterilant.
Preparation method with the substituted pyridines methyl phosphoramidate of general formula I-1 expression makes the represented compound of general formula (II)
(Y is identical with the definition in the general formula (I) in the formula) and the represented compound of following general formula (III)
(R in the formula
1, R
2, X is with identical with the definition in the general formula (I)) react (A method).
In the above-mentioned reaction, dialkoxy or alcoxyl aryloxy phosphoryl chloride (III) are 1～1.25: 1 with the amount proportioning of the reactant species of 2-replacement-5-aminomethyl-pyridine (II), reaction solvent adopts chloroform, organic solvents such as methylene dichloride, ethylene dichloride, benzene, acetone, ethyl acetate, in the presence of basic catalyst pyridine or tertiary amine, 0～50 ℃ of reaction 4-6 hour, can obtain yield preferably.When III is alcoxyl aryloxy phosphoryl chloride, adopt alkoxyl group phosphinylidyne dichloro and phenol sodium solution 0～20 ℃ of reaction 30～60 minutes, direct and II reaction without separating alcoxyl aryloxy phosphoryl chloride.
Preparation method with the substituted pyridines thiomethyl phosphorothionate of general formula I-2 expression makes the represented compound of general formula (IV)
(Y is identical with the definition in the general formula (I) in the formula) and the represented compound of following logical formula V
(R in the formula
1, R
2Identical with the definition in the general formula (I) with X, M represents Na, K, Ca, NH
4Positively charged ion) reacts (B method)
In the above-mentioned reaction, dioxane (virtue) oxygen base or alkoxyl group aryloxy thiophosphate (V) are 1: 1～1.35 with the amount proportioning of the reactant species of 2-replacement-5-chloromethylpyridine (IV), being reflected at aqueous phase carries out, 10～90 ℃ of temperature of reaction, 1～4 hour reaction times, after reaction is finished, the reaction solution extracted with diethyl ether, extraction liquid washes with water, precipitation behind the dry extraction liquid.
Be described more specifically the preparation method of compound in (I-1) in the compound of (I) of the present invention formula, (I-2) formula below by embodiment.
Embodiment 1
Preparation (A method)
0.02mol phenol is dissolved in 2.7g30%NaOH solution produces the phenol sodium solution, about 15 ℃, be added drop-wise to 0.02molMeOP (S) Cl
2In, at room temperature stirred after dripping off 1 hour, add 0.03molEt again
3N drips the acetone soln of 10ml0.02mol 2-chloro-5-aminomethyl-pyridine simultaneously, reacts under the room temperature 4～5 hours, and reaction finishes, and the solids removed by filtration material is used Thin-layer separation after the concentrating filter liquor, and pure product are white needle-like crystals, yield 82%, m.p.80～82 ℃
Ultimate analysis: measured value C% 47.07 H% 4.46 N% 8.59
Calculated value C% 47.56 H% 4.27 N% 8.54
IR(cm
-1)?3268(γ
N-H)， 3049(γ
Ph-H)，?1203(γ
P-O-Calkyl)
1039(γ
P-O-Calkyl)，921(γ
P-N)， 746(γ
p＝s)
1HNMR (δ, and ppm) 1.60～1.86 (wide, 1H, NH), 3.76 (d, 3H, OCH
3)
4.22(dd，2H，-CH
2)，7.12～7.32(m，5H，-C
6H
5)
7.56～8.28(m，3H，C
5H
3N)
Embodiment 2
Preparation (A method)
With 0.02mol (MeO) (EtO) P (S) Cl, 0.03mol Et
3N is dissolved in the 10ml acetone, and 15 ℃ of 20ml acetone solns that drip 0.02mol 2-chloro-5-aminomethyl-pyridine of temperature control drip off the back and continue to stir under this temperature 3～5 hours.Reaction finishes, and the solids removed by filtration material is used Thin-layer separation after the concentrating filter liquor, and pure product are weak yellow liquid, yield 87%, n
D 201.5481
Ultimate analysis: measured value C% 38.32 H% 4.81 N% 10.31
Calculated value C% 38.57 H% 5.00 N% 10.00
IR(cm
-1) 3268(γ
N-H)，2976(γ
C-H)，1052(γ
P-O-Calkyl)，928(γ
P-N)，745(γ
P＝S)
1HNMR (δ, ppm) 1.07 (t, 3H, CH
3CH
2), 1.96～2.10 (wide, 1H, NH),
3.64(dd，3H，-OCH
3)，4.02(m，2H，OCH
2CH
3)，
4.22 (d, 2H ,-CH
2), 7.22～8.28 (m, 3H, C
5H
3N) embodiment 3
Preparation (A method)
With 0.02mol (MeO)
2P (S) Cl, 0.03mol Et
3N is dissolved in 15 ℃ of 20ml acetone solns that drip 0.02mol 2-chloro-5-aminomethyl-pyridine of temperature control in the 10ml acetone, drips off the back and continues to stir under this temperature 3～5 hours, and reaction finishes, the solids removed by filtration material, filtrate is used Thin-layer separation, and pure product are weak yellow liquid, yield is 91%, n
D 201.5529
Ultimate analysis measured value C% 36.27 H% 4.62 N% 10.75
Calculated value C% 36.09 H% 4.51 N% 10.53
IR(cm
-1) 3271(γ
N-N)，2991(γ
C-H)，1054(γ
P-O-Calkyl)，924(γ
P-N)，740(γ
P＝S)
1HNMR(δ，ppm)3.20(S，1H)，3.51(d，6H)，4.13(d，2H)，7.30～8.29(m，3H)
Embodiment 4
Preparation (B method)
The 0.33mol diisopropyl phosphite is dissolved in the 100ml benzene, add 0.34mol sublimed sulphur and 0.17mol CaO again, keep 70～90 ℃ of temperature of reaction, stirring reaction all dissolves until sulphur and becomes faint yellow transparent solution, with the salt that the distilled water extraction generates, the calcium salt yield is 95.0%.Again calcium saline solution is gone in the three-necked flask, add 0.32mol 2-chloro-5-chloromethylpyridine, 80 ℃ of following stirring reactions 1～2 hour.After reaction is finished, use the extracted with diethyl ether product, extraction liquid washes with water, uses Na
2SO
4Dry back precipitation, crude product separates with column chromatography, gets yellow thick liquid, yield 86.0%, n behind the purifying
D 151.5019
Ultimate analysis measured value C% 44.53 H% 5.91 N% 4.11
Calculated value C% 44.58 H% 5.88 N% 4.33
IR(cm
-1) 3060(γ
Ph-H) 2950(γ
C-H) 1240(γ
p＝0)
990(γ
P-O-C) 695(γ
C-Cl) 650(γ
C-S)
1HNMR(δppm)1.28(q，12H，2(CH
3)
2CHO-)，4.44～4.84(m，2H，2?O?CH(CH
3)
2)
4.00(d，2H，SCH
2)，7.60～8.30(m，3H，-C
5H
3N)
Embodiment 5
Preparation (B method)
With 0.03mol (MeO) (EtO) P (S) Cl be dissolved in 20ml1,4-dioxane and 5mlH
2In the mixed solvent of O, add the 10ml aqueous solution of 0.06molNaOH preparation again, 100 ℃ of reactions of temperature control are until PH=7～8 o'clock termination reaction.The 2-chloro-5-chloromethylpyridine that adds 0.03mol again in reaction mixture was 90 ℃ of following stirring reactions 3 hours.After finishing, reaction uses 10%K
2CO
3The aqueous solution is neutralized to neutrality.Use organic solvent extraction, crude product separates with column chromatography behind the precipitation.Pure product are yellow thick liquid, yield 89%, n
D 201.5009
IR(cm
-1)3070(γ
ph-H)，2950(γ
C-H)，1245(γ
P＝O)，1012(γ
P-O-C)
693(γ
C-Cl)，649(γ
C-S)
1HNMR(δ，ppm)1.31(t，3H，-OCH
2CH
3)，3.78(d，3H，-OCH
3)，4.00(d，2H，
SCH
2)，4.00～4.30(m，2H，-O?CH
2CH
3)，7.28～8.33(m，3H，
C
5H
3N)
Embodiment 6
With 0.03mol
Be dissolved in 20ml1,4-dioxane and 5ml
2In the mixed solution of O, add the 10ml aqueous solution of 0.06mol NaOH preparation again, temperature control reacts to PH=7～8 o'clock termination reaction for 100 ℃, adds the 2-chloro-5-chloromethylpyridine of 0.03mol again in reaction mixture, 90 ℃ of following stirring reactions 3 hours, after finishing, reaction uses 10%K
2CO
3The aqueous solution is neutralized to neutrality.Use organic solvent extraction, crude product separates with column chromatography behind the precipitation.Pure product are light yellow solid, yield 40%, m.p.63 ℃.
IR(cm
-1)3030(γ
ph-H)，2925(γ
C-H)，1260(γ
p＝0)，1160(γ
P-O-C)，693(γ
C-Cl)，630(γ
C-S)
1HNMR(δ，ppm)2.3(S，6H，2CH
3)，3.98(d，2H，SCH
2)，7.02(d，8H)，7.04(d，1H)
7.36～7.46(dd，1H)，8.14(d，1H)
M/e 419(4.27％)
Adopt above-mentioned similar approach can prepare other compound equally.Listedly in the table 1 be synthetic part of compounds of the present invention.
The implication of ellipsis: Me---methyl in the table, Et---ethyl, n-Pr---n-propyl, i-Pr---sec.-propyl, n-Bu---normal-butyl, i-Bu-2---methyl-propyl, S-Bu-1---methyl-propyl, n-Am---n-pentyl, Ph---phenyl, 4-MePh---p-methylphenyl 2,4-Cl
2Ph---2, the 4-dichlorophenyl
Table 1
No. R
1 R
2 X Z Y
1 Me Ph S NH Cl
2 Et Ph S NH Cl
3 n-Pr Ph S NH Cl
4 Me 4-MePh S NH Cl
5 Et 4-MePh S NH Cl
6 n-Pr 4-MePh S NH Cl
7 Me 2，4-Cl
2Ph S NH Cl
8 Et 2，4-Cl
2Ph S NH Cl
9 n-Pr 2，4-Cl
2Ph S NH Cl
10 Me Me S NH Cl
11 Me Et S NH Cl
12 Me n-Pr S NH Cl
13 Et Et S NH Cl
14 Et n-pr S NH Cl
15 n-Pr n-Pr S NH Cl
16 n-Pr n-Pr O S Cl
17 Et Et O S Cl
18 i-Pr i-Pr O S Cl
19 i-Bu i-Bu O S Cl
20 S-Bu n-Bu O S Cl
21 n-Bu n-Bu O S Cl
22 n-Am n-Am O S Cl
23 Me Et O S Cl
24 Me n-Pr O S Cl
25 Et n-Pr O S Cl
26 Et Ph O S Cl
27 Et 4-MePh O S Cl
28 4-MePh?4-MePh O S Cl
29 n-Pr n-Pr O S H
30 Et Et O S H
31 i-Pr i-Pr O S H
32 i-Bu i-Bu O S H
33 S-Bu S-Bu O S H
34 n-Bu n-Bu O S H
35 n-Am n-Am O S H
From following test as can be seen, the compound of formula of the present invention (I) has the stronger activity of killing to aphid and red spider.
Embodiment 7
Kill broad bean aphid test (pickling process)
Cut the broad bean cauline leaf of band aphid (fundatrix of casting off a skin the same day), immerse in the soup to be measured of the 250ppm prepare in advance, flood 5 second the back cover lampshade (preventing that aphid from fleeing in disorder) that starts, place in 25 ± 2 ℃ the growth cabinet, if blank, 24 hours " Invest, Then Investigate " death condition are calculated mortality ratio.Table 2 is the measurement result of part (I) formula compound.
Table 2
No. R
1R
2X Z Y mortality ratio/%
5 Et 4-MePh S NH Cl 87.8
6 n-Pr 4-MePh S NH Cl 66.3
7 Me 2，4-Cl
2Ph S NH Cl 91.3
8 Et 2，4-Cl
2Ph S NH Cl 67.4
9 n-Pr 2，4-Cl
2Ph S NH Cl 96.2
15 n-Pr n-Pr S NH Cl 97.5
17 Et Et O S Cl 78.0
23 Me Et O S Cl 100.0
24 Me n-Pr O S Cl 100.0
25 Et n-Pr O S Cl 100.0
26 Et Pr O S Cl 85.7
30 Et Et O S H 100.0
When compound of the present invention uses as sterilant, can be with carrier or the mixing diluents that allows in compound of the present invention and other plant protection, whereby it is modulated into normally used various formulation, as pulvis, granule, aqueous emulsion waits and uses, and also can mix with other agricultural chemicals such as sterilant, sterilant, miticide, weedicide, plant-growth regulator etc. to use or simultaneously and use.
Embodiment 8
Kill red spider test (pickling process)
Get frame bean seedlings with 2 true leaves, connecting the blade that has red spider places sunlight to remove listless leaf after following 1 hour, cut band red spider bean seedlings, in the soup to be measured of 250ppm, soaked for 3 seconds, then the frame bean seedlings are all inserted in the Erlenmeyer flask that is filled with water, establish blank, place 25 ± 2 ℃ growth cabinet, after 24 hours, investigation adult death condition is calculated mortality ratio under anatomical lens.Table 3 is the measurement result of part (I) compound.
Table 3
No R
1R
2X Z Y mortality ratio/%
8 Et 2，4-Cl
2Ph S NH Cl 88.9
23 Me Et O S Cl 77.5
24 Me n-Pr O S Cl 85.8
27 Et 4-MePh O S Cl 65.5
31 i-Pr i-Pr O S H 77
When compound of the present invention uses as miticide, can be with carrier or the mixing diluents that allows in compound of the present invention and other plant protection, whereby it is modulated into normally used various formulation, wait as pulvis, granule, aqueous emulsion and to use, also can mix and use or simultaneously and use with other agricultural chemicals such as sterilant, sterilant, miticide, weedicide, plant-growth regulator etc.
Claims (7)
1, a class substituted picolyl phosphoric acid easter, (I) structure expressed that it is characterized in that having general formula
In the formula: R
1, R
2Expression C
1～C
5Alkyl, phenyl or substituted-phenyl, substituting group is halogen, nitro, methyl
R
1With R
2Identical or inequality
X represents O or S
Z represents S or NH
Y represents H or Cl
2, as claimed in claim 1 by the substituted pyridines methyl phosphoramidate general formula in the compound of general formula (I) expression
Preparation method's (A method), it is characterized in that making the represented compound of general formula (I)
(Y is identical with the definition of claim 1 in the formula) and the represented compound of following general formula (II)
(R in the formula
1, R
2Identical with X with the definition in the claim 1) react.
3, the synthetic reaction condition of compound as claimed in claim 2 (I-1), it is characterized in that: dialkoxy or alcoxyl aryloxy phosphoryl chloride and 2-replacement-5-aminomethyl-pyridine amount of substance proportioning are 1～1.25: 1, mineral alkali or organic alkali as a catalyst, temperature of reaction is 0～50 ℃, and the reaction times is 4～6 hours.
4, as claimed in claim 1 by the substituted pyridines methyl thiolophosphate general formula in the compound of general formula (I) expression
Preparation method's (B method), it is characterized in that making the represented compound of general formula (IV)
(Y is identical with the definition of claim 1 in the formula) and the represented compound of following logical formula V
(R in the formula
1, R
2Identical with the definition in the claim 1 with X, M represents Na, K, Ca, NH
4Positively charged ion) reacts.
5, the synthetic reaction condition of compound as claimed in claim 4 (I-2), it is characterized in that: the amount of substance proportioning of dioxane (virtue) oxygen base or alcoxyl aryloxy thiophosphate and 2-replacement-5-chloromethylpyridine is 1: 1～1.35,10～90 ℃ of temperature of reaction, 1～4 hour reaction times.
6, the substituted picolyl phosphoric acid easter application of compound with general formula (I) expression as claimed in claim 1 is characterized in that the effective ingredient as sterilant.
7, the substituted picolyl phosphoric acid easter application of compound with general formula (I) expression as claimed in claim 1 is characterized in that as acaricidal effective ingredient.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97109262A CN1094127C (en) | 1997-10-06 | 1997-10-06 | Substituted picolyl phosphoric acid easter with insecticidal activity and its prepn. method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97109262A CN1094127C (en) | 1997-10-06 | 1997-10-06 | Substituted picolyl phosphoric acid easter with insecticidal activity and its prepn. method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1213664A CN1213664A (en) | 1999-04-14 |
| CN1094127C true CN1094127C (en) | 2002-11-13 |
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ID=5171069
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97109262A Expired - Fee Related CN1094127C (en) | 1997-10-06 | 1997-10-06 | Substituted picolyl phosphoric acid easter with insecticidal activity and its prepn. method |
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|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100467478C (en) * | 2005-09-15 | 2009-03-11 | 浙江工业大学 | Thiophosphate or phosphate derivative and its prepn and application |
| CN102503979B (en) * | 2011-10-14 | 2015-07-29 | 华中师范大学 | There is the phosphamide compound of flame retardant properties and preparation thereof and application in the epoxy |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0307502A1 (en) * | 1985-03-25 | 1989-03-22 | Dowelanco | Process for preparing phosphorothioates and phosphates |
-
1997
- 1997-10-06 CN CN97109262A patent/CN1094127C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0307502A1 (en) * | 1985-03-25 | 1989-03-22 | Dowelanco | Process for preparing phosphorothioates and phosphates |
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