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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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims description 16
- 238000000034 method Methods 0.000 title claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims description 8
- 230000000749 insecticidal effect Effects 0.000 title abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- -1 nitro, methyl Chemical group 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 230000000895 acaricidal effect Effects 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000004615 ingredient Substances 0.000 claims description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl chloride Substances ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 2
- 239000000126 substance Substances 0.000 claims 2
- 239000002585 base Substances 0.000 claims 1
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- 241001124076 Aphididae Species 0.000 abstract description 5
- 241000488583 Panonychus ulmi Species 0.000 abstract description 5
- 239000000642 acaricide Substances 0.000 abstract description 4
- 230000002147 killing effect Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- 239000002917 insecticide Substances 0.000 abstract 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical class COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 abstract 1
- 125000001424 substituent group Chemical group 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XPARFBOWIYMLMY-UHFFFAOYSA-N (6-chloropyridin-3-yl)methanamine Chemical compound NCC1=CC=C(Cl)N=C1 XPARFBOWIYMLMY-UHFFFAOYSA-N 0.000 description 3
- SKCNYHLTRZIINA-UHFFFAOYSA-N 2-chloro-5-(chloromethyl)pyridine Chemical compound ClCC1=CC=C(Cl)N=C1 SKCNYHLTRZIINA-UHFFFAOYSA-N 0.000 description 3
- 125000006414 CCl Chemical group ClC* 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 244000046052 Phaseolus vulgaris Species 0.000 description 3
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 240000006677 Vicia faba Species 0.000 description 2
- 235000010749 Vicia faba Nutrition 0.000 description 2
- 235000002098 Vicia faba var. major Nutrition 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000005648 plant growth regulator Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 235000014347 soups Nutrition 0.000 description 2
- 241000894007 species Species 0.000 description 2
- MTXSIJUGVMTTMU-JTQLQIEISA-N (S)-anabasine Chemical compound N1CCCC[C@H]1C1=CC=CN=C1 MTXSIJUGVMTTMU-JTQLQIEISA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 239000005906 Imidacloprid Substances 0.000 description 1
- 206010024642 Listless Diseases 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229930014345 anabasine Natural products 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- NFORZJQPTUSMRL-UHFFFAOYSA-N dipropan-2-yl hydrogen phosphite Chemical compound CC(C)OP(O)OC(C)C NFORZJQPTUSMRL-UHFFFAOYSA-N 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 208000035475 disorder Diseases 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 description 1
- 229940056881 imidacloprid Drugs 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
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。
A class of substituted picolyl methyl phosphates with insecticidal activity and a preparation method thereof belong to the technical field of fine organic synthesis. Substituted picolyl phosphate with insecticidal activity of the general 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 remarkable killing activity on aphids or red spiders, and can be used as insecticide or 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 |
Family
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| 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 | A phosphorothioate or phosphate derivative and its preparation 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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|---|---|
| CN1213664A (en) | 1999-04-14 |
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