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CN1213664A - 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 PDF

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CN1213664A
CN1213664A CN 97109262 CN97109262A CN1213664A CN 1213664 A CN1213664 A CN 1213664A CN 97109262 CN97109262 CN 97109262 CN 97109262 A CN97109262 A CN 97109262A CN 1213664 A CN1213664 A CN 1213664A
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CN1094127C (en
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刘钊杰
胡利明
卿湘华
贺红武
肖尚友
邓胜娄
严刚
周青春
陆爱红
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Central China Normal University
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Abstract

一类具有杀虫活性的取代吡啶甲基磷酸酯及其制备方法,所属技术领域为精细有机合成。通式为右式的具有杀虫活性的取代吡啶甲基磷酸酯,式中R1、R2表示C1～C5的烷基、苯基、取代苯基(取代基为卤素,硝基,甲基),R1与R2相同或者不相同,X表示O或者S,Z表示S或者NH,Y表示H或者Cl。本化合物对蚜虫或红蜘蛛具有显著的杀灭活性,可用作杀虫剂或杀螨剂。

Figure 97109262

A class of substituted picolyl methyl phosphates with insecticidal activity and a preparation method thereof belong to the technical field of fine organic synthesis. The general formula is the substituted picolyl methyl phosphate with insecticidal activity of the right formula, where R 1 and R 2 represent C 1 ~ C 5 alkyl, phenyl, substituted phenyl (substituents are halogen, nitro, methyl), 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 significant killing activity against aphids or red spiders, and can be used as an insecticide or acaricide.

Figure 97109262

Description

Has substituted picolyl phosphoric acid easter of insecticidal activity and preparation method thereof
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)
Figure A9710926200041
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 I of the present invention comprises with the represented substituted pyridines methyl phosphoramidate of following formula I-1; Substituted pyridines thiomethyl thiolophosphate with formula I-2 expression.
Figure A9710926200042
R in the formula 1, R 2, in X, Y and the formula I definition identical
The compound of above-mentioned formula I provided by the invention 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 formula I-1 expression makes the logical represented compound of formula II
Figure A9710926200043
(Y is identical with the definition in the logical formula I in the formula) and the represented compound of following logical formula III (R in the formula 1, R 2, X is with identical with the definition in the logical 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 formula I-2 expression makes the logical represented compound of formula IV
Figure A9710926200053
(Y is identical with the definition in the logical formula I in the formula) and the represented compound of following general formula (V)
Figure A9710926200054
(R in the formula 1, R 2Identical with the definition in the logical formula I with X, M represents Na, K, Ca, NH 4Positively charged ion) reacts (B method)
Figure A9710926200055
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
Figure A9710926200061
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 10ml 0.02mol 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
Figure A9710926200062
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
Figure A9710926200071
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
Figure A9710926200072
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 96.0%, 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=o)
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,2OCH(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 20ml 1,4-dioxane and 5ml H 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,-OCH 2CH 3),7.28～8.33(m,3H,
C 5H 3N)
Embodiment 6
Figure A9710926200081
Preparation (B method)
With 0.03mol
Figure A9710926200082
Be dissolved in 20ml 1,4-dioxane and 5ml H 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=o),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 in the table: Me-methyl, 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-2,4-dichlorophenyl
Table 1No. R 1R 2X 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 Cl5 Et 4-MePh S NH Cl6 n-Pr 4-MePh S NH Cl7 Me 2,4-Cl 2Ph S NH Cl8 Et 2,4-Cl 2Ph S NH Cl9 n-Pr 2,4-Cl 2Ph S NH Cl10 Me Me S NH Cl11 Me Et S NH Cl12 Me n-Pr S NH Cl13 Et Et S NH Cl14 Et n-pr S NH Cl15 n-Pr n-Pr S NH Cl16 n-Pr n-Pr O S Cl17 Et Et O S Cl18 i-Pr i-Pr O S Cl19 i-Bu i-Bu O S Cl20 S-Bu n-Bu O S Cl21 n-Bu n-Bu O S Cl22 n-Am n-Am O S Cl23 Me Et O S Cl24 Me n-Pr O S Cl25 Et n-Pr O S Cl26 Et Ph O S Cl27 Et 4-MePh O S Cl28 4-MePh 4-MePh O S Cl29 n-Pr n-Pr O S H30 Et Et O S H31 i-Pr i-Pr O S H32 i-Bu i-Bu O S H33 S-Bu S-Bu O S H34 n-Bu n-Bu O S H35 n-Am a-Am O S H
From following test as can be seen, the compound of formula I of the present invention 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 2No. R 1R 2X Z Y mortality ratio/%5 Et 4-MePh S NH Cl 87.86 n-Pr 4-MePh S NH Cl 66.37 Me 2,4-Cl 2Ph S NH Cl 91.38 Et 2,4-Cl 2Ph S NH Cl 67.49 n-Pr 2,4-Cl 2Ph S NH Cl 96.215 n-Pr n-Pr S NH Cl 97.517 Et Et O S Cl 78.023 Me Et O S Cl 100.024 Me n-Pr O S Cl 100.025 Et n-Pr O S Cl 100.026 Et Pr O S Cl 85.730 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 3No R 1R 2X Z Y mortality ratio/%8 Et 2,4-Cl 2Ph S NH Cl 88.923 Me Et O S Cl 77.524 Me n-Pr O S Cl 85.827 Et 4-MePh O S Cl 65.531 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、一类新型取代吡啶甲基磷酸酯，其特征在于具有通式(Ⅰ)表达的结构式中：R1、R2表示C1～C5的烷基、苯基或者取代苯基，取代基为卤素、硝基、甲基1. A new type of substituted picolyl phosphate, characterized in that it has a structure expressed by general formula (I) In the formula: R 1 and R 2 represent C 1 to C 5 alkyl, phenyl or substituted phenyl, and the substituents are halogen, nitro, methyl R1与R2相同或不相同R 1 is the same or different from R 2 X表示O或者SX means O or S Z表示S或者NHZ means S or NH Y表示H或ClY stands for H or Cl 2、如权利要求1所述的由通式(Ⅰ)表示的化合物中的取代吡啶甲基磷酰胺酯通式 2. The general formula of the substituted picolylphosphoramidate in the compound represented by the general formula (I) as claimed in claim 1 的制备方法(A法)，其特征是使通式(Ⅱ)所表示的化合物
Figure A9710926200023
(式中Y与权利要求1的定义相同)与下述通式(Ⅲ)所表示的化合物
Figure A9710926200024
(式中R1、R2和X与权利要求1中的定义相同)进行反应。The preparation method (A method), is characterized in that the compound represented by general formula (II)
Figure A9710926200023
(Y in the formula is the same as the definition of claim 1) and the compound represented by the following general formula (III)
Figure A9710926200024
(wherein R 1 , R 2 and X are as defined in claim 1) to react. 3、如权利要求2所述的化合物(Ⅰ-1)的合成反应条件，其特征是：二烷氧基或烷氧芳氧基磷酰氯与2-取代-5-氨甲基吡啶物质的量配比为1～1.25∶1，无机碱或有机碱作催化剂，反应温度为0～50℃，反应时间为4～6小时。3. The synthesis reaction conditions of compound (I-1) as claimed in claim 2, characterized in that: the amount of dialkoxy or alkoxy aryloxy phosphorus oxychloride and 2-substituted-5-aminomethylpyridine The ratio is 1-1.25:1, the inorganic base or organic base is used as the catalyst, the reaction temperature is 0-50°C, and the reaction time is 4-6 hours. 4、如权利要求1所述的由通式(Ⅰ)表示的化合物中的取代吡啶硫甲基硫赶磷酸酯通式
Figure A9710926200025
的制备方法(B法)，其特征是使通式(Ⅳ)所表示的化合物
Figure A9710926200026
(式中Y与权利要求1的定义相同)与下述通式(Ⅴ)所表示的化合物(式中R1、R2和X与权利要求1中的定义相同，M表示Na、K、Ca、NH4阳离子)进行反应。4. Substituted pyridylthiomethyl phosphorothioate in the compound represented by general formula (I) as claimed in claim 1
Figure A9710926200025
The preparation method (B method), is characterized in that the compound represented by general formula (IV)
Figure A9710926200026
(in the formula, Y has the same definition as claim 1) and the compound represented by the following general formula (Ⅴ) (wherein R 1 , R 2 and X are as defined in claim 1, and M represents Na, K, Ca, NH 4 cations) to react. 5、如权利要求4所述的化合物(Ⅰ-2)的合成反应条件，其特征是：二烷(芳)氧基或烷氧芳氧基硫代磷酸盐与2-取代-5-氯甲基吡啶的物质的量配比为1∶1～1.35，反应温度10～90℃，反应时间1～4小时。5. The synthetic reaction conditions of the compound (I-2) as claimed in claim 4, characterized in that: dialkyl (aryl)oxy or alkoxy aryloxy phosphorothioate and 2-substituted-5-chloroform The substance ratio of pyridine is 1:1-1.35, the reaction temperature is 10-90° C., and the reaction time is 1-4 hours. 6、如权利要求1所述的以通式(Ⅰ)表示的取代吡啶甲基磷酸酯化合物的应用，其特征是作为杀虫剂的有效成份。6. The application of the substituted picolyl phosphate compound represented by the general formula (I) as claimed in claim 1, characterized in that it is used as an active ingredient of an insecticide. 7、如权利要求1所述的以通式(Ⅰ)表示的取代吡啶甲基磷酸酯化合物的应用，其特征是作为杀螨剂的有效成份。7. The application of the substituted picolyl phosphate compound represented by the general formula (I) as claimed in claim 1, characterized in that it is used as an active ingredient of an acaricide.
CN97109262A 1997-10-06 1997-10-06 Substituted picolyl phosphoric acid easter with insecticidal activity and its prepn. method Expired - Fee Related CN1094127C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100467478C (en) * 2005-09-15 2009-03-11 浙江工业大学 A phosphorothioate or phosphate derivative and its preparation and application
CN102503979A (en) * 2011-10-14 2012-06-20 华中师范大学 Phosphamide compound with flame retardance and preparation method and application thereof to epoxy resin
CN119119122A (en) * 2024-09-12 2024-12-13 烟台大学 A method for preparing meta-phosphonylated polysubstituted pyridine compounds

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU602917B2 (en) * 1985-03-25 1990-11-01 Dow Chemical Company, The Processes for preparing of phosphorothioates and phosphates

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100467478C (en) * 2005-09-15 2009-03-11 浙江工业大学 A phosphorothioate or phosphate derivative and its preparation and application
CN102503979A (en) * 2011-10-14 2012-06-20 华中师范大学 Phosphamide compound with flame retardance and preparation method and application thereof to epoxy resin
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
CN119119122A (en) * 2024-09-12 2024-12-13 烟台大学 A method for preparing meta-phosphonylated polysubstituted pyridine compounds
CN119119122B (en) * 2024-09-12 2025-09-09 烟台大学 Preparation method of meta-phosphonated polysubstituted pyridine compound

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