CN86101647A - S, the preparation of S-dithio tertiary butyl ethyl phosphine acid esters and as the application of agricultural chemicals - Google Patents

S, the preparation of S-dithio tertiary butyl ethyl phosphine acid esters and as the application of agricultural chemicals Download PDF

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CN86101647A
CN86101647A CN198686101647A CN86101647A CN86101647A CN 86101647 A CN86101647 A CN 86101647A CN 198686101647 A CN198686101647 A CN 198686101647A CN 86101647 A CN86101647 A CN 86101647A CN 86101647 A CN86101647 A CN 86101647A
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compd
compound
tertiary butyl
dithio
soil
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斯坦利·索马斯·德里克·高夫
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May and Baker Ltd
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4075—Esters with hydroxyalkyl compounds

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  • Pest Control & Pesticides (AREA)
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Abstract

The present invention relates to S, S-dithio tertiary butyl ethyl phosphine acid esters and it for example can be used for control of maize root first as the purposes of sterilant and nematocides.

Description

S, the preparation of S-dithio tertiary butyl ethyl phosphine acid esters and as the application of agricultural chemicals
The present invention relates to S, S-dithio tertiary butyl ethyl phosphine acid esters and the pesticide composition that constitutes as activeconstituents by it and as the purposes of sterilant and nematocides.
Compound of the present invention has structural formula CH 3CH 2-P(=O) (SC(CH 3) 3) 2(I) shown the desinsection and the nematicide activity of wide spectrum to have advantages of excellent stability, and long residual effect is especially arranged in soil.
This compound can be used to kill adult, larva and the worm's ovum of lepidopteran (butterfly and moth), for example Heliothis virescens of Heliothis, bollworm and so on agricultural; The african armyworm that mythimna separata belongs to, egyptian cotton prodenia litura, subtropics mythimna separata, tippet mythimna separata and so on; The real moth of the cotton spot that real moth belongs to; The pink bollworm of Pectinophora spp; The Pyrausta nubilalis (Hubern). that the wild snout moth's larva of rice belongs to, cabbage looper and so on; Pier (wild cabbage white butterfly); Noctua (mythimna separata): the ground tiger belongs to (cutworm); Wisena belongs to (porina); Straw borer spp (striped rice borer); Yellow rice borer belongs to and sugarcane borer belongs to (sugarcane borer and rice borer); Pilleriana, apple Du moth; Fruit tree volume moth belongs to small cabbage moth.Also can be used to kill adult and the larva of Coleoptera, for example the brown little Du of coffee cherry; Become mildewed pseudo-chrysomelid genus, cotton boll resembles; The chrysomelid genus of cucumber; The mud Eimeria; Phyllotreta, colorado potato bug; Chrysomelid genus (corn root A); The latent Eimeria (pseudo-wireworm) of soil; Click beetle belongs to (wireworm), skin Du worm, flour gold tortoise; The xylotrupes dichotomus belongs to (grub), horseradish daikon leaf beetle, Lissorhoptrus oryzophilus Kuschel; Nitidulid belongs to (pollen beetle); Weevil belongs to (moth root weevil); The root nodule weevil belongs to (pea and soybean nodulation weevil).Also can be used to kill the insect of Hemiptera, for example Psylla spp; Aleyrodes; Aphis; Tumor aphid genus, repair the tail aphid; Phylloxera spp; Adelgid belongs to, hops wart volume aphid; Aeneolamia belongs to; Rice green leafhopper belongs to; Empoasca spp belongs to; Brown paddy plant hopper belongs to; Plant hopper (plant hopper) belongs to; The sugarcane plant hopper belongs to; The circle a red-spotted lizard belongs to (California red scale); A red-spotted lizard belongs to; Mealybug belongs to; Fleahopper belongs to; Tarnished plant bug belongs to; Red stinkbug belongs to; Chinch bug belongs to; Bemisia spp.Also can be used to kill hymenopteran insect, for example tenthredinidae and basic honeybee belong to; Leaf cutting ant belongs to.Can be used to kill dipterous insect, for example Hylemyia; The awns horn fly belongs to; Hippelates flavipes belongs to; Liriomyza belongs to; Anastrepha.To Thysanoptera cotton thrips for example; Orthoptera is migratory locusts and grasshopper genus for example; For example field criet belongs to cricket spp, acheta domestica belongs to, mole cricket; Collembola is Entomobrya and Onychiurus arcticus genus for example; Isoptera is Cryptotermes for example; The Dermaptera arthropods that for example ball Sou belongs to and other agricultural is relevant is mite section (Tetranychus, Panonychus citri genus, Bryobia, recover mite belong to, eat more tarsonemid mite and belong to) for example; Julid belongs to; Common house centipede belongs to damp Eimeria and apus belongs to (Crustachia); And to invading and harassing the nematode Cyst nematode (Heterodera, Globidium) for example that farming is root and tender shoots; Ma Shi golden nematode (root nodule Turbatrix); Hinder root nematode (root Turbatrix); The nematode (Ditylenchus) of coffee thorn root Turbatrix and infringement stem and ball base etc. all has killing action.
Because compound of the present invention is active good to killing of corn root A (chrysomelid genus), residual effect is long in soil, so this compound is particularly conducive to control of maize root first.Its residual effect time limit in soil has surpassed the compound of similar chemical structure unexpectedly, and this is confirmed by the experimental result of being recorded and narrated in the following example 1.
Example 1: experiment
Test has general formula I A structure with compound:
R（X）P（＝X 1）（X 2R 1）（X 3R 2） （IA）
Compound R (X) X 1X 2R 1X 3R 2
A ethyl-O S the tertiary butyl S tertiary butyl
B ethyl-O S n-propyl S the tertiary butyl
C ethyl-O S sec.-propyl S the tertiary butyl
D ethyl-O S isobutyl-S the tertiary butyl
E ethyl-O S normal-butyl S the tertiary butyl
F methyl-O S n-propyl S the tertiary butyl
G ethyl-S S tertiary butyl O sec.-propyl
H ethyl-S S the tertiary butyl O tertiary butyl
The I ethyl O O S tertiary butyl S tertiary butyl
J ethyl O O S tertiary butyl S sec-butyl
Compound
A is compound of the present invention,
B is a United States Patent (USP) 4,472, the compound of numbering 2 in 390,
C is a United States Patent (USP) 4,472, the compound of numbering 7 in 390,
D is a United States Patent (USP) 4,472, the compound of numbering 9 in 390,
E is a United States Patent (USP) 4,472, the compound of numbering 10 in 390,
F is a United States Patent (USP) 4,472, the compound of numbering 12 in 390,
G is a United States Patent (USP) 4,268, the example 8 in 508.
H is a United States Patent (USP) 4,268, the similar compound of compd A in 508
I is the compound of numbering 11 among the PCT number of patent application WO83/008870,
J is the compound of numbering 10 among the PCT number of patent application WO83/008870.
Residual effect and persistent mensuration to corn root A (chrysomelid genus)
Measuring method
Used soil is a kind of clay loam, and containing the 23%(oven-dried weight that moisture is about oven-dried weight is that pedotheque is 110 ℃ of weight that record after oven dry in 24 hours).The consumption of all test compounds is all represented with the ppm number of oven-dried weight soil.Before handling soil with test compound, the sieve with 3.5 millimeters eyelets sieves soil earlier.
Test compound is dissolved in the acetone, is mixed with prescribed concentration, makes to add 1 ml soln after be equivalent in the 100 gram oven-dried weight soil samples, and this compound concentrations is 0.1 and 0.5ppm, can also be 0.05ppm sometimes.
The soil samples that are equivalent to 500 gram oven-dried weights are placed in the polyethylene plastic bag, and the acetone soln of the test compound of prescribed concentration is added in the bag for 5 milliliters, make thorough mixing.Opened sack then one hour, and allowed acetone vapor away.
Soil sampling is also carried out the activity test (0 day) to cucumber 11 asterophyllite first immediately from plastics bag.With this soil in 24 ℃ of dark-coloured glass guide channels that are stored in sealing, and after handling soil the 7th, 14,21,28,42,56,70 and 84 day with test compound, further sampling test (7,14,21,28,42,56,70 and 84 days) should be mixed soil before each sampling once more respectively.
Chrysomelid activity is followed these steps to measure:
Chrysomelidly on the corn seedling, cultivate at 25 ℃.
About 20 restrain the soil of handling puts in one 25 * 75 millimeters the vial, bottle includes 2.5 ml distilled waters and a germination corn seedling that has well-developed root, the chrysomelid larva of cultivating 5 days is placed on above the soil, if have through the several minutes earth borer of failing and go into the larva of soil, then it is replaced, up to whole larvas all earth borer go among the soil.Test tube covers with a wire cloth, keeps 4 days at 25 ℃.Four parallel samples are made in each test, and until doing the 42nd day (comprising 42 days), the 56th, 70 is each with two parallel samples with 84 days test.After four days, check whole samples, and count the larva number of dying and living, the average mortality of larva calculates according to the result of four parallel samples, and compares with undressed control group.
Average mortality just shows that more than or equal to 90% the chrysomelid genus larva of control reaches satisfied effect.
Experiment gained result lists in table I and table II.
Figure 86101647_IMG1
Figure 86101647_IMG3
Can see from The above results:
(1) when concentration is 0.1ppm, compd A has shown the promising result of preventing and treating chrysomelid larva, and is longer more than 6 times than the persistence of compd B.Compd A has shown satisfied prevention effect until 42 days, but compd B to 7 day just can not provide satisfied prevention effect.Even during concentration big 5 times (0. 5ppm), compd B did not just reach satisfied effect yet between 28 days and 42 days.Even when compd A concentration is hanged down to 0.05ppm, still can reach promising result until 14 days, but mention,, just not reach promising result to 7 days even compd B concentration is its twice (during 0.1ppm) as top.
(2) when concentration is 0.1ppm, the persistence that compd A is prevented and treated chrysomelid larva is more than 6 times of Compound C, and compd A still can have promising result until 42 days, and Compound C to 7 a day average mortality ratio has been lower than 90%.When concentration was 0.05ppm, compd A still can have satisfied effect until 14 days, and Compound C in addition at the beginning (0 day) does not just reach promising result.
(3) even when concentration is 0.5ppm, it is not good enough that Compound D to 28 day is prevented and treated the effect of chrysomelid larva, and in contrast, and when compd A only was 1/5th (0.1ppm) in concentration, still can effect until 42 days satisfied, persistence be the twice of Compound D.When concentration is 0.1ppm, though Compound D at the beginning (0 day) do not reach promising result yet, and compd A also can provide promising result until 42 days when this concentration, even when concentration is 0.05ppm, still can promising result until 14 days.
(4) when concentration is 0.5ppm, compd E is prevented and treated the effect to 7 of chrysomelid larva and day just can not be satisfied with, even and compd A when 0.1ppm, persistence was more than 6 times of compd E, until 42 days.Even concentration is when being 0.05ppm, and compd A is prevented and treated persistence and still is the twice of 0.5ppm compd E, is until 14 days.When concentration 0.1ppm, compd E (0 day) does not at the beginning just almost have activity, and compd A is still satisfied until 42 days effects, even concentration reduces by 1/2nd to 0.05ppm, can also reach promising result until 14 days compd As.
(5) when concentration is 0.5ppm, it is not good enough until 14 days that compound F 17-hydroxy-corticosterone is prevented and treated the effect of chrysomelid larva, and compd A is when 0.1ppm concentration, still promising result can be arranged until 42 days, persistence is its 3 times at least, even concentration is reduced to 1/10th (0.05ppm), compd A still can have promising result until 14 days, and persistence is at least than the long twice of 0.5ppm compound F 17-hydroxy-corticosterone.When concentration is 0.1ppm, though compound F 17-hydroxy-corticosterone at the beginning (0 day) just do not reach promising result, still effect was satisfied until 42 days and compd A is in this concentration, (0.05ppm) can also reach promising result until 14 days compd As even concentration reduces by half.
(6) compound G and compound H are prevented and treated the effect of chrysomelid larva, when concentration is 0.5ppm and 0.1ppm, even at the beginning (0 day) they all do not reach promising result, and compd A is when 0.1ppm and 0.05ppm, respectively until 42 days or still can effect until 14 days satisfied.
When (7) concentration is 0.1ppm, chemical compounds I prevent and treat chrysomelid larva at the beginning (0 day) dissatisfied with regard to effect, and when this concentration compd A still effect was satisfied until 42 days, even concentration is reduced to 1/5th (0.05ppm), compd A can also reach promising result until 14 days.When concentration is 0.5ppm, chemical compounds I to 56 day can not provide promising result, and compd A still can provide promising result until 84 days when this concentration, even when concentration was reduced to 1/5th (0.1ppm), its persistence and chemical compounds I were similar when concentration is 0.5ppm.
(8) even when concentration is 0.5ppm, compound J prevents and treats chrysomelid larva to 14 day just can not provide promising result, and compd A concentration is reduced to 1/5th (0.1ppm), and persistence is its three times at least, can also provide promising result to 42 days.When concentration was reduced to 1/10th (0.05ppm), still effect was satisfied until 14 days for compd A.When concentration was 0.1ppm, (0 day) just can not go out promising result to compound J at the beginning, and compd A still can effect be satisfied with until 42 days when this concentration, even when concentration was 0.05ppm, still effect was satisfied until 14 days.
(9) be 0.1ppm in concentration, compd A prevent and treat persistence that chrysomelid larva can reach promising result be in the control compounds (compd B and Compound C) persistence the longest more than six times, that is at least 42 days; And compd B and C just can not provide promising result to 7 days when this concentration, though all the other seven kinds of control compounds at the beginning (0 day), none can provide promising result.
The data of chrysomelid larva average mortality showed when (10) concentration was 0.1ppm21 days, 28 days and 42 days in the table I, and the activity of compd A is six times of Compound C in the time of 21 days, were nine times of Compound D; In the time of 28 days, the activity of compd A is nine sesquialters of Compound C, is 19 times of Compound D; All the other seven kinds of control compounds are during to these days, all loss of activity; And 42 days the time, compd A still can reach chrysomelid larva average mortality 90%, and total loss activity during all the other nine kinds of control compounds to 42 day.
Result that table I and table are listed in the II clearly illustrated compd A aspect the chrysomelid persistence of control and in the fixed time at administered compound to chrysomelid active aspect, compare with nine kinds of control compounds and to have unexpected substantial advantage.This point is especially more obvious behind the result of analytical test compound gained during in 0.1ppm concentration, the compd A control is chrysomelid still can to provide promising result at least to 42 days, and control compounds C is dissatisfied with regard to effect in the time of 14 days in this concentration, control compounds B is not good enough with regard to effect in the time of 7 days, and (0 day) just can not provide promising result to all the other seven kinds of control compounds at the beginning.Even concentration improves five times when reaching 0.5ppm, also have only two kinds of control compounds (Compound C and I) to provide that satisfied persistence is almost grown with the persistence of compd A when concentration is 0.1ppm or a little longer; Compound C and I to 56 day is not good enough with regard to effect, and compd A surpasses 84 days and still can provide satisfied prevention effect when concentration is 0.5ppm.
Following example 2 will further be illustrated S to example 7, desinsection that S-dithio tertiary butyl ethyl phosphine acid esters (compd A) is valuable and nematicide characteristic.
Example 2: to field corn control of maize root first
It is 10% granule that compd A is made concentration, and when the drilling corn, it is applied in the soil of the field corn of being invaded and harassed by corn root A, later on corn crop is extracted with root, the root of observing them is subjected to the degree of damage of corn root A (chrysomelid genus), adopt the common root grade evaluation of being injured, 6.0 expressions are subjected to insect and invade and harass greatly, and 1.0 expressions do not see that infringement is arranged.The consumption of compd A is represented (kg/ha) with how many kilograms of per hectare, and the result is as follows: amount of application (kg/ha), the root grade of being injured
The parallel test plot mean
Compd A A B C D
0.84????2.1????2.2????2.1????1.8????2.05
0.56????2.6????2.1????2.4????1.9????2.25
0.28????2.8????2.8????2.9????2.3????2.70
Blank group 5.9 5.9 4.9 3.6 5.08
Compare with the result of blank group (unprocessed control), the compd A and the processing ensuing crop root extent of damage are little, have shown the efficient of this compound control of maize root first.
3 pairs of field corn control of maize of example kind maggot
It is 20% granule that compd A is made into concentration, soil to the field corn zone invaded and harassed by corn kind maggot, it is applied in bar (band) or the ditch (in-furrow), and the amount of application of compd A is 1.12kg/ha, and time of application is to carry out at seeding time.Handle the effect of control of maize kind maggot (planting fly), can measure along the number of bar ditch discovery fly pupa by counting later on.The fly pupa number scale of finding in the fly pupa number of finding in the zone of handling and the unprocessed zone is become percentage ratio.The result is as follows:
Compd A (1.12kg/ha) control district finds fly pupa percentage ratio (%)
Drilling handles 15
Trench sowing handles 30
The fly pupa reduces 85% and 70% respectively, shows that compd A has the high reactivity of control of maize kind maggot.
The control of mole cricket in 4 pairs of turfs of example
It is 20% granule that compd A is made into concentration, is applied in to be subjected on the turf that mole cricket (Gryllotalpidae) invades and harasses, and the compd A amount of application is equivalent to 5.6kg/ha and 11.2kg/ha.Caused the number of soil ridge before and after the recording processing by mole cricket, the result is as follows:
Compd A is handled unprocessed
（kg/ha）
5.6????11.2
Soil ridge number
Handle preceding 13.8 7.3
Handle back 2.8 8.3
Handle preceding 10.3 15.0
Handle back 1.5 17.0
Handle back soil ridge number and greatly reduce, show that compd A is powerful aspect the control mole cricket than before handling.
5 pairs of lands for growing field crops of example legume crop control pealeaf weevil and soybean weevil larva
It is 10% granule that compd A is made into concentration, invades and harasses the soil application compd A around the legume crop of spring sowing land for growing field crops in the zone to being subjected to pealeaf weevil and soybean weevil, and amount of application all is respectively 1kg/ha and 2kg/ha in twice experiment.The parallel test district has four in the experiment 1, and the parallel test district has three in the experiment 2.After seven weeks, crop is extracted with root approximately, calculate the quantity of root weevil larva.Note with the relatively back average percentage that reduces of the larva number on the unprocessed control group crop, the result is as follows:
The average percentage (%) that compd A (kg/ha) larva number reduces
2 experiments, 1 experiment 2
90.2????92
1????53.3????93.75
Administered compound A greatly reduces the larva number, and the result of the experiment 2 when experiment 1 when particularly amount of application is 2kg/ha and experiment 2 and amount of application are 1kg/ha shows, the effect of compd A control pealeaf weevil and soybean weevil larva.
Example 6 is measured the test of the white grub effect of control sugarcane
Compd A is dissolved in the acetone, and gained solution is used to handle the soil of some amount, makes the concentration of compd A in soil reach specified numerical value.After solvent evaporation was fallen, the soil of handling left (every alms bowl has 110 gram soil approximately) in the glass alms bowl in.Corresponding each concentration value is prepared 20 glass alms bowls.Every alms bowl is placed some of the larvas of the white grub of sugarcane (Fu Shi flour gold tortoise) in 1/3rd length of times, checks the mortality ratio of larva after 28 days, and the result is as follows:
The amount of application mortality ratio (%) of compd A
(mg/kg soil) (proofreading and correct with the control group result)
0.5????47
1.0????89
2.0????95
4.0????100
8.0????100
The gained result shows that compd A has high insecticidal activity to the white grub of sugarcane.
The test that example 7 control nematodes live
(a) corn Ditylenchus dipsaci
Nematode is cultivated on the alfalfa plant in greenhouse.After inoculation 2～3 months, the results plant is immersed in its cauline leaf cut-out in the water, washes ovum and the larva of nematode from cauline leaf.Be prepared into the inoculation suspension that contains 150 larvas of having an appointment in every ml distilled water after sieving.
The soil of not being infected with is screened into 1～2 millimeter-sized particles, then with river sand balanced mix.Compd A is dispersed in the distilled water by means of tween 80 in advance, this dispersion liquid is added in a collection of soil to be tested goes, and make the dilute strength of compd A in soil reach claimed range.
200 milliliters plastic tub is partly put undressed coarse sand granule earlier into, 100 alfalfa seeds of every basin sowing.And then put chemically treated soil, the undressed soil of the sample of blank group into.All 5 milliliters of nematode suspension pourings in the above, each basin has been accepted about 750 larvas to each basin like this.Plastic tub remains under the humidity of suitable seed germination and plant-growth.
After 12～14 days, the situation of nematode infringement is gathered and checked to clover grain seedling.Each validity of handling is represented with the percentage ratio that the infringement with the comparison of blank group reduces.The result is as follows for secondary experiment gained:
Invading of compd A amount of application and the comparison of blank group
The percentage ratio (%) that evil reduces
(kg/ha) experiment 1 experiment 2
100????100????-
50????100????100
25????80????100
10????50????70
5????50????80
1????-????60
("-" expression when this amount of application " in this experiment do not do experiment ")
(b) Root of Roundpod Jute wart nematode
Nematode is cultivated on the tomato plant in greenhouse.Washing, immersion tomato root, and the process sieve series gets the Root of Roundpod Jute wart nematode standard inoculation suspension that contains 1500 pieces of worm's ovums in every ml distilled water approximately.At least the ovum of 10-15% is to be in embryo's larval stage.
Experiment with soil be by the river sand of equivalent, peat soil and not the soil of pickup manually mix and make.Soil is to reach every liter of soil with enough worm egg suspension inoculations to contain 30,000 pieces of ovum approximately.Compd A is dissolved in the acetone and is absorbed on a small amount of attapulgite (Attaclay), vapors away acetone then.Except that the soil of blank group, each batch soil is all added the attapulgite of handling, and makes the dilute strength of test compound in soil meet the requirements of scope after manually mixing.
The every batch of soil is contained in two flowerpots of doing parallel test, waters and preserves two week in a humid environment.Then two tomato seedling are transplanted into respectively in each basin, are placed in the greenhouse and kept again for four weeks.
The tomato herborization is got up the number of washing and calculating root nodule.Each effect of handling represents that with the percentage ratio of comparing the minimizing of root nodule number with the blank group twice experimental result is as follows:
The compd A amount of application compares root nodule with the blank group
The percentage ratio (%) that reduces
(kg/ha) experiment 1 experiment 2
100????100????-
50????100????100
25????100????100
10????100????90
5????50????0
1????-????0
("-" expression when this amount of application " in this experiment do not do experiment ")
The above results shows that compd A has high activity to the corn Ditylenchus dipsaci, and Root of Roundpod Jute wart nematode is had very high activity.
Compound of the present invention can prepare (said in this specification sheets " known in fact method " this term is meant and has been used at present or the existing method of narrating) by known in fact method in chemical literature.Compound of the present invention is a raw material with ethyl phosphine acyl fontanel preferably, and ethyl phosphine acyl fontanel and 2-first propyl group-2-mercaptan are reacted in the presence of alkali, makes this compound.
According to characteristics of the present invention, the compound of structure formula I is by ethyl phosphine acyl fontanel CH 3CH 2-P(=0) (X)-X 1X represents a fontanel plain atom, preferably chlorine atom in (general formula II) formula; X 1Represent the plain atom of a fontanel, preferably chlorine atom, or uncle's butylthio [SC(CH 3) 3], work as X 1Represent the plain atomic time of fontanel, the 2-first propyl group-2-mercaptan of it and 2 molar equivalents reacts in the presence of alkali; Work as X 1When representing uncle's butylthio, it and 1 molar equivalent 2-first propyl group-2-mercaptan react in the presence of alkali, or an alkali metal salt of it and mercaptan for example sodium salt react.
Reaction process is undertaken by following reaction formula A and B:
Reaction formula A(X 1Represent a halogen atom)
（ⅡA）
（Ⅰ）
Reaction formula B[X 1Representative-SC(CH 3) 3]
（ⅡB）
（Ⅰ）
X and X in the formula 1Implication such as above-mentioned regulation.
The reaction of describing among the reaction formula A is more suitable in being used for preparing the compound that the structural formula I is represented.
Reaction process is preferably in temperature and is about 0～100 ℃, in a kind of organic solvent, with a kind of by mercaptan and basic metal for example the mercaptan an alkali metal salt that makes of sodium or its hydride, oxyhydroxide (as sodium hydroxide) react.
Appropriate organic solvent for example has benzene, toluene, hexanaphthene, tetrahydrofuran (THF), dimethyl formamide, butanone-2 and acetone.
The compound of general formula II can prepare with known in fact method.For example the method that can record and narrate with people such as Morita of the compound of general formula II A [Tetrahedron Letters, 28,2522-6(1978); Chemistry Letters(1980), 435-8,1,374,757 and Pianfetti and Quin at J.Amer.Chem.Soc., 84,851(1962)] in the method recorded and narrated prepare.The compound of general formula II B can be prepared by the method for recording and narrating among the UK Patent Application No 2087891A.2-first propyl group-2-mercaptan can prepare (Dobbin, J.Chem, Soc., 57,641) by the method that Dobbin records and narrates.
Compound of the present invention can be used as sterilant and/or nematocides effectively when lower concentration.Because effectively dispensary needs the amount of compound very little, can not directly take compound to use usually.Therefore this compound need be used with the composition forms of sterilant or nematocides, composition contains S, S-dithio tertiary butyl ethyl phosphine acid esters, preferably make it to be dispersed on one or more compatible mutually agriculturals among receptible diluent or carrier and/or the tensio-active agent (that is to say that these diluent or carriers and/or tensio-active agent can be applicable to sterilant or nematicidal agent composition in prior art, and with active ingredient can be compatible).
Constituting the composition that can use by active compound of the present invention can be dispersion liquid or emulsion, wherein contains about 0.001% to the 1%(weight/volume of active compound).Because active compound is water insoluble in essence, therefore the organic solvent that needs to add inert, plant-less toxicity is made concentrated solution, wherein preferably contain 2～75%(weight/volume of having an appointment) active compound, and this concentrated solution easily is dispersed in the aqueous media, thereby forms the homodisperse liquid of the active compound that can use.Said composition also contains tensio-active agent usually.For example, effective liquid composition can be made up of this active compound, acetone or alcohol, water and a kind of tensio-active agent such as tween 20 (polyoxygenated ethylidene Arlacel-20) or any other suitable tensio-active agent.
The composition that contains this active compound also can be solid form, for example pulvis or granule.For instance, active compound can mix mutually with suitable solid carrier such as kaolinite, bentonite, talcum etc.; Perhaps mix in the suitable particle, for example mineral clay such as attapulgite, montmorillonite, diatomite, sepiolite.Dust composition is to contain 0.5～25%(w/w of having an appointment) active compound for well; Granule composite is to contain 1～25%(w/w of having an appointment) active compound for well.
The composition that contains active compound also can contain other farm chemical ingredients, and for example other sterilant, nematocides and sterilant resemble hexanone oxime prestige, furans pellet, aldicarb and F-1991 and so on.
In order to prevent and treat insect and nematode, usually active compound is applied in the place that needs control insect or nematode to invade and harass, amount of application is generally on the per hectare processing area with about 0.1～25 kilogram active compound.In ideal conditions, depend on the insect that will prevent and treat, perhaps lower amount of application just can reach appropriate protection.On the other hand, disadvantageous climatic condition, resistance of insect and other factors may require the active ingredient amount of application higher.
When insect is when growing in soil, the preparation that contains active compound can any mode be easily evenly executed and is sprinkled upon in the zone that needs handle.As required, dispenser can be sprinkled upon in the field or in the plant growth zone, perhaps very approaching seed to be protected or the place of plant.Can in the dispenser zone, sprinkle water active ingredient washed in the soil and go, or by natural rainy effect.During the dispenser or afterwards, as required, pesticide preparation can for example plow or rake the soil level by mechanical dispersion in soil.Using medicine can be before plantation, during plantation, after the plantation, but will avoid before germinateing or after germinateing.
The preparation of following example explanation The compounds of this invention:
Example 8:S, the preparation of S-dithio tertiary butyl ethyl phosphine acid esters
With sodium hydride (3.0 gram, 0.125 mole) 0 ℃ be suspended in exsiccant tetrahydrofuran (THF) (70 milliliters) among.In 15 minutes, drip 2-first propyl group-2-mercaptan (14.1 milliliters, 0.125 mole) then, and keep temperature to be lower than 5 ℃.The gained mixture at room temperature stirs and spends the night, and adds the ethyl phosphine acyl dichloro (7.35 grams, 0.05 mole) that is dissolved among the dry tetrahydrofuran (10 milliliters) in 30 minutes, and keeps temperature to be lower than 35 ℃ with the water-bath cooling.The gained mixture at room temperature stirred 5 hours, placed then and spent the night.
Add toluene (200 milliliters) earlier, at Jia Shui (200 milliliters), standing demix.Toluene layer washs with 2N aqueous sodium hydroxide solution (100 milliliters), water (100 milliliters) washing again, and drying, filtration, evaporation make S then, and S-dithio tertiary butyl ethyl phosphine acid esters (8.72 gram) is oily, yield 69%.
Making the structure of product [marks in the tetramethylsilane work, at the unimodal [SC(CH in 1.6ppm place with its phosphorus nuclear magnetic resonance spectrum (is that benchmark occurs unimodal at the 65.0ppm place with 85% phosphoric acid) and hydrogen nuclear magnetic resonance spectrum 3) 3], be two triplet peak (P-CH at 1.1ppm and 1.3ppm place 2-CH 3) and a multiplet peak (P-CH is arranged at the 2.2ppm place 2CH 3)] can confirm.The integrated curve of hydrogen nuclear magnetic resonance spectrum conforms to the structure of description.
The composition that the explanation of following example produces according to the present invention:
Example 9: a kind of granular composition includes:
S, S-dithio tertiary butyl ethyl phosphine acid esters ... the 10%(w/w)
Propylene glycol ... the 5%(w/w)
Attapulgite 24/48 order particle ... the 85%(w/w)
Press the method preparation, with S, S-dithio tertiary butyl ethyl phosphine acid esters and mixed with propylene glycol, are sprayed at compound on the attapulgite particle under the pressure of 2 crust by a flat fan nozzle, mix in a horizontal mixing drum simultaneously.After whole spray liquid finished, mixing must continue all to be absorbed until liquid, till the uniform particles about ten minutes.The granule that makes thus can be applied in by the zone of chrysomelid genus infest, and its amount of application is 3 kilograms of per hectares.
Contain the 20%(w/w) S, the granule of S-dithio tertiary butyl ethyl phosphine acid esters, available similar approach makes.

Claims (4)

1, a kind of preparation S, the method for S-dithio tertiary butyl ethyl phosphine acid esters is characterized in that general formula is CH 3CH 2-P[=0] the ethyl phosphine carboxylic acid halides of [X]-X ', X represents a halogen atom in the formula, X ' represents a halogen atom or uncle's butylthio, when X ' represents a halogen atom, 2-first propyl group-2-mercaptan with 2 molar equivalents, or when X ' represented uncle's butylthio, the 2-first propyl group-2-mercaptan with 1 molar equivalent reacted in the presence of alkali.
2, a kind of method of preventing and treating insect and nematode is characterized in that the S to these insects or their habitat applying pesticides consumption, S-dithio tertiary butyl ethyl phosphine acid esters.
3, a kind of method of control of maize root first is characterized in that the S of applying pesticides consumption in soil, S-dithio tertiary butyl ethyl phosphine acid esters.
4, a kind of composition is characterized in that it by the S as sterilant or nematocides significant quantity, and organic solvent or a kind of solid carrier of S-dithio uncle Dingruo's ethyl phosphine acid esters and a kind of inertia, plant-less toxicity are formed.
CN198686101647A 1985-02-21 1986-02-19 S, the preparation of S-dithio tertiary butyl ethyl phosphine acid esters and as the application of agricultural chemicals Pending CN86101647A (en)

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US4752604A (en) * 1985-07-29 1988-06-21 Stauffer Chemical Company S,S-di-(tertiary alkyl) thiophosphonate insecticides
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