CN85105807A - The preparation method of novel aromatic compounds - Google Patents
The preparation method of novel aromatic compounds Download PDFInfo
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- CN85105807A CN85105807A CN 85105807 CN85105807A CN85105807A CN 85105807 A CN85105807 A CN 85105807A CN 85105807 CN85105807 CN 85105807 CN 85105807 A CN85105807 A CN 85105807A CN 85105807 A CN85105807 A CN 85105807A
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Abstract
The present invention's molecular formula of touching upon is the preparation method of the novel cpd of I, and the implication of each symbol provides in specification sheets and claims in the formula, and molecular formula is the purposes (in order to Pest Control such as insect, mite and tick) of the compound of I.
Description
The touch upon preparation method of the novel aromatic compounds that is used for Pest Control of the present invention.Though many agent for controlling noxious insect pests are on record as IGR compound Entocon ZR 515, hydroprene and fenoxycarb, be necessary the compound that adopts more effective IGR compound (for example more active compound) and/or have the various not same sexes.
The invention provides molecular formula is the novel compound of I,
In the formula, m and m ' are respectively 0 or 1;
N is 0,1,2 or 3;
R is the alkyl of 1-8 carbon atom, the alkenyl of a 2-8 carbon atom, the alkynyl of a 2-8 carbon atom, the haloalkyl of a 1-8 carbon atom, the halogenated alkenyl of a 2-8 carbon atom, the halo alkynyl of a 2-8 carbon atom, the alkoxyalkyl of a 2-10 carbon atom, the alkyl-thio-alkyl of a 2-10 carbon atom, the cycloalkyl of a 3-8 carbon atom, the halogenated cycloalkyl of a 3-8 carbon atom, cycloalkylalkyl, Heterocyclylalkyl or the Heterocyclylalkyl alkyl of a 4-12 carbon atom;
R
1, R
2, R
3, R
4And R
8Be respectively the alkyl of a hydrogen or 1-8 carbon atom;
R
7Alkyl for 1-8 carbon atom, the alkenyl of 2-8 carbon atom, the alkynyl of 2-8 carbon atom, the haloalkyl of 1-8 carbon atom, the halogenated alkenyl of 2-8 carbon atom, the halo alkynyl of 2-8 carbon atom, the cycloalkyl of 3-8 carbon atom, the cycloalkylalkyl of 4-12 carbon atom, 1, in 2 or 3 annular carbon atoms by the alkyl of 1-8 carbon atom, the haloalkyl of 1-8 carbon atom, the alkoxyl group of 1-8 carbon atom, the halogenated alkoxy of 1-8 carbon atom, halogen, nitro, the alkylthio group of a cyano group and 1-8 carbon atom replaces or unsubstituted phenyl; When X ' is NR
9The time, R
7Also can be and replace or unsubstituted thio-phenyl and S-C(CH
3)
2-CN group; R
9For hydrogen or be selected from R
Group;
W is oxygen, sulphur, NR
8, CR
R
4Or carbonyl;
W ' is oxygen, sulphur, NR
, CR
R
4, carbonyl, sulfinyl or alkylsulfonyl;
X is oxygen, sulphur or NR
8;
X ' is oxygen, sulphur or NR
9;
Y is oxygen, sulphur or NR
8; And
Z is the alkyl of hydrogen, a 1-8 carbon atom, the haloalkyl or the halogen of a 1-8 carbon atom.
Molecular formula is the vital role that the compound of I has Pest Control, particularly has the performance of control insect.
Molecular formula of the present invention is that the compound of I can prepare with currently known methods, for example United States Patent (USP) 4080470 and 4215139 and European patent 98800 in those method for makings of introducing, now be summarized as follows.A kind of easy method comprises: make molecular formula be O-, the S-of the compound of I or N-alkylation or-amino, alkoxyl group, phenoxy group or the sulfo-part of acidylate and other parts that molecular formula is the compound of I generate a kind of (sulfo-) ethers, (sulfo-) ester, amine or (sulfo-) acid amides.Usually this method can be carried out under the condition in order to preparation (sulfo-) ether, (sulfo-) ester, amine or (sulfo-) acid amides; be raw material promptly, with known O-, S-or N-alkylation or O-, S-or N-process for acylating preparation (sulfo-) ether, amine, (sulfo-) carbamate, (sulfo-) urea and (sulfo-) carbonate with corresponding alcohol, phenol, sulphur alkohol and amine.The reagent of suitable O-, S-or N-alkylation and O-, S-or N-acidylate is that molecular formula is halogenide (for example alkyl-or acyl halide) or its active functional derivative of III, VI, VIII, IX or X (seeing below); for example, an alkali metal salt (is the compound of IX as molecular formula) of methylsulfonyl salt (is the compound of VIII as molecular formula), (sulfo-) carboxylic acid and different (sulfo-) cyanate (is the compound of IV as molecular formula).
Molecular formula is that preparation method's (suitable example) of the compound of I comprises:
(a) making molecular formula is the compound of II and the reaction of compound that molecular formula is III, and the molecular formula II is:
M, m ', n, R, W ', Z, W, R in the formula
1, R
2, R
3R
4With the definition of X as above, the molecular formula III is:
Y, X in the formula
1And R
7Definition as above, Q is a halogen;
(b) making molecular formula is that compound that compound and the molecular formula of II (definition as above) is IV reacts that to make molecular formula be I
aCompound, the molecular formula I
aFor:
M, m in the formula
1, n, R, W
1, Z, W, R
1, R
2, R
3, R
4, X and R
7Definition as above, Y
1Be O or S, the molecular formula IV is as follows:
Y in the formula
1And R
7Definition as above;
(c) making molecular formula is that to make molecular formula be I for the compound of V and the reaction of compound that molecular formula is VI
bCompound, the molecular formula I
bFor:
W in the formula
aBe O, S or NR
2, m, n, R, W ', Z, R
1, R
2, R
3, R
4, X, Y, X
1, R
7And R
8Definition as above, the molecular formula V is:
M, R, W ', Z and W in the formula
aDefinition as above,
The molecular formula VI is:
N in the formula, Q, R
1, R
2, R
3, R
4, X, Y, X
1And R
7Definition as above;
(d) making molecular formula is that to make molecular formula be I for the compound of VII and the reaction of compound that molecular formula is VIII
cCompound, the molecular formula I
cFor:
W in the formula
' aBe O, S or NR
8, m ', n, R, Z, W, R
1, R
2, R
3, R
4, X, Y, X
1, R
7And R
8Definition as above, the molecular formula VII is:
M ', n, W in the formula
' a, Z, W, R
1, R
2, R
3, R
4, X, Y, X
1And R
7Define as above, the molecular formula VIII is:
Wherein, the definition of R as above, Q is halogen or methylsulfonyl;
(e) making molecular formula is that to make molecular formula be I for the compound of IX and the reaction of compound that molecular formula is X
dCompound, the molecular formula I
dFor:
M, n, R, W ', Z, W, R in the formula
1, R
2, R
3, R
4, X, Y, X ' and R definition as above, the molecular formula IX is:
Q in the formula
aBe OM, SM or halogen, M is a kind of basic metal, m, m ', n, R, W ', Z, W, R
1, R
2, R
3, R
4, X and Y definition as above, the molecular formula X is:
In the formula, Q
bCan be halogen (Q wherein
aBe OM or SM) or can be wherein Q of OM or SM(
aBe halogen), R
7Definition as above.
Above-mentioned reaction itself is known, and the condition of reacting is known to those skilled in the art.A kind of organic solvent (this solvent is an inert under reaction conditions), as carrying out above-mentioned reaction easily in N-Methyl pyrrolidone, dimethyl formamide or the tetrahydrofuran (THF).
Suitable reaction temperature is-5 °-140 ℃, as 10 ° and 110 ℃.
A kind of reactant in the above-mentioned reaction is a halogenide, generally has been preferably in alkali (as K
2CO
3Or NaOH) reacts under the situation, or halogenide and the salt (as sodium salt) of alcohol, phenol, benzenethiol or amine or (sulfo-) carboxylic acid are reacted.
Recyclable molecular formula is the compound of I from reaction mixture (step is operated and the reaction mixture that generates in accordance with regulations).
Molecular formula of the present invention is that the compound of I has one or more symmetric carbon atoms.The present invention also comprises the various optical isomers and the racemic mixture thereof of these compounds.Among the embodiment hereinafter, unless otherwise indicated, the compound that makes is a kind of racemic mixture.
In the aforesaid method, used raw material and reagent are known, but also unknown to some degree, available above-mentioned similar method or make with similar currently known methods.
R is the alkyl of 1-8 carbon atom, the alkenyl of a 2-8 carbon atom or the alkynyl of 2-8 carbon atom, refers in particular to have 2-6 carbon atom alkyl, alkenyl or the alkynyl of (4 or 5 carbon atoms are better); These groups are preferably branched.When R is alkyl, be preferably 2-methyl-butyl, especially the 2-butyl.When R was alkenyl, being preferably 3-methyl-2-butene base (was CH
3C(CH
3)=CHCH
2).
Haloalkyl, the halogenated alkenyl of a 2-8 carbon atom, the halo alkynyl of a 2-8 carbon atom, the halogenated cycloalkyl of a 3-8 carbon atom and the halogenated alkoxy of 1-8 carbon atom of so-called 1-8 carbon atom are meant the alkyl that is replaced by 1-6 (especially 1-3) halogen atom.Halogen is chlorine or fluorine preferably.
If when adopting alkenyl and alkynyl, the meaning is meant that these alkyl have 1 or 2 (best 1) ethylene linkage respectively or 1 or 2 (best 1) acetylene bond is arranged).
So-called " Heterocyclylalkyl " is meant a kind of heterocycloalkyl, and be saturated or undersaturated, 2-6 carbon atom arranged, 1-3 nitrogen, oxygen or sulphur atom.So-called " Heterocyclylalkyl alkyl " is meant a kind of heterocycloalkyl, and one of them hydrogen atom is replaced by a low alkyl group, and the total number of carbon atoms is 3-12.
Molecular formula is that the compound of I preferably has following one or more features:
R is the alkyl of 1-8 carbon atom or the alkenyl of 2-8 carbon atom, is preferably the alkyl of 1-8 carbon atom.
M is preferably 1.
W ' is O, S, NH or Co, for O, S or Co are better, for O or S best.
Z is H, halogen, CH
3Or CF
3, be preferably H.
W is O or S, is preferably O.
M ' is preferably 1.
R
1, R
3Or R
8All can be the alkyl of 1-8 carbon atom, be generally the alkyl of 1-5 carbon atom, be preferably CH
3
R
2And R
4Be preferably H.
X is the alkyl of O, S, a NH or N(1-5 carbon atom), be preferably O or NH.
N is preferably 1.
X ' is the alkyl of S, O, a NH or N(1-5 carbon atom), be preferably the alkyl of S, O, a NH or N(1-2 carbon atom).
R
7Be the alkyl of 1-8 carbon atom, the cycloalkyl of 3-6 carbon atom, the alkyl of the alkenyl of 3-5 carbon atom or single halo-1-5 carbon atom, R
7For the alkyl of 1-5 carbon atom, as CH
3, C
2H
5, C
3H
7, be preferably CH
3Or C
2H
5
Y is preferably O or S.
Molecular formula is the compound of I, preferably includes carbamate and thiocarbamate (that is, X and X in the molecular formula I that molecular formula is an I
1Be the compound of O or S, if X
1Then all the other are NR for O or S
3, if X is O or S, then all the other are NR
9; Molecular formula is an I in seeing below
fCompound).Obviously above-mentioned specific selectivity is applicable to that also molecular formula is an I
fCompound, the molecular formula I
fMiddle x is NR
8, R
8Be preferably hydrogen, X
1Be NR
9, R
9Be preferably H, CH
3Or C
2H
5
CR
1R
2-(CR
3R
4) n part preferably contains 2-3 carbon atom, n is preferably 1, and m and m ' preferably are 1.
The molecular formula of making by short-cut method is the compound of I, and its usage comprises: with the molecular formula of insect pest manipulated variable is that the compound of I is sprayed at insect (insect, mite, tick) and goes up or be sprayed at insects and grow the place.
For those of ordinary skill, laboratory test by routine is easy to determine that molecular formula is the optimum amount of the compound of I, usually, when the test dose of each insect, mite or tick is 0.1 microgram-100 microgram, can obtain gratifying result, this is not only relevant with the kind of insect, but also relevant with use-pattern and working conditions.
Molecular formula is that the compound of I all has activity for many insects, for example, and the ovum of flea (ctenocephalides felis), tick, fly (housefly), cockroach, blatta germanica, noctuid kind etc.In view of above-mentioned activity, these compounds can be used as the insects control agent effectively, for example, in order to control following insects: the tick of lepidopteran, Hemiptera, Homoptera, Coleoptera, Diptera, Orthoptera and flea wing order and other insect, mite, acarina, comprise the mite of Tetranychidae or apart from the mite of line mite section, the tick of the tick of Argasidae and hard tick section.
To be that the compound of I can influence insects abnormal and then differently cause that it is dead or make insects irreproducible in view of molecular formula, preferably to immature insect, promptly dives worm's ovum phase, embryonic stage, larva and apply this compound pupa time.For many molecular formula is the compound of I, and its efficient is equal to or less than commercially available known IGR compound, as, Entocon ZR 515, hydroprene etc.Because molecular formula is the compound of I insect is had control action kou, therefore can be used for protection, the forest of farm crop protection, store the protection of protection, livestock and the animalcule of cereal, also can be used for eradication of cockroaches etc.
Useful especially compound is as follows: Table A, B and C during compd A-19, A-21, A-39, A-88, B-7, B-26, B-31, B-34, especially compd A-1, A-13, A-14, A-30, A-31, A-36, A-38, A-40, A-82, A-83, A-86, B-1, B-9, B-12, B-14, B-17, B-19, B-25, B-29, B-32, B-33 and C-10(see below).
With molecular formula is that compound and a kind of mixing diluents of I can be made pest controllers easily.The present invention comprises that also by molecular formula be the composition that the compound of I is formed.These compositions are that the compound of I is done outside the promoting agent divided by molecular formula, also contain other promoting agent, for example sterilant (as, synthetic pyrethroid, carbamate, phosphoric acid ester), insect growth control agent or attractant.During use, said composition can be solid form or liquid form (but as be the wet-milling form or be the emulsible strong solution form of the common thinner of a kind of adding).Available usual way makes these compositions (for example, with active constituent and a kind of thinner and other optional batching, mixing as tensio-active agent).
Used thinner be meant can be added in the active constituent generate be suitable for or expection activity intensity and any liquid or agricultural easy to use go up the solid that is suitable for, as talcum, kaolin, diatomite, dimethylbenzene or water.
The batching that is used to spray (but as the dispersible strong solution of water or wet-milling) contains tensio-active agent (as wetting agent and dispersion agent), for example, the condensation product of formaldehyde and naphthalenesulfonate, a kind of alkylaryl sulphonate, a kind of Sulfite lignin, a kind of fatty alkyl sulfuric ester, a kind of ethoxylated alkylphenol and a kind of fatty alcohol ethoxylate.
Usually, prescription comprises: 0.01-90%(by weight, promoting agent down together), the tensio-active agent and 99.99%-10%(solid or the liquid that are suitable on the 0-20% agricultural) thinner, promoting agent contains compound that a kind of molecular formula is an I at least or is the compound of I and the mixture that other promoting agent is formed by molecular formula.Spissated composition generally contains promoting agent and is about 2-90%(and preferably is about 5-65%), contain promoting agent 0.01-2.5%(in the actual batching of using and preferably contain 0.01-50%) or rarer solution; Its usage comprises: the form that injection, aerosol producer, bait lure, encapsulate, cyclodextrin comprise complex compound, desinsection disk, little ring, ear hoop, mythimna separata agglomerate and analogue.
It is in order to further specify the present invention that following example purpose is provided.Temperature in the example is a degree centigrade, and umber and percentage number average are by weight.R
TBe meant room temperature.
The example of composition:
Emulsifiable concentrates:
With 65 parts of molecular formula compound that is I (for example, the compd A that hereinafter provides-1) with 8 parts of emulsifying agents (as 4 parts of Atlox3404F and 4 parts of Atlox848, this is the negatively charged ion of American I CI and the mixture of nonionic emulsifier) and 27 parts of organic solvents (as dimethylbenzene or field nanogram 500-100, this is the mixture of the xylene solvent of a kind of Three methyl Benzene and field Nanogram Corp.) thorough mixing up to making a kind of uniform solution.
Example 1: ethyl n-2-(4-(3-methyl-2-butene oxygen base) phenoxy group)-the 1-methylethyl } (method is a) for carbamate.
At 5 ℃ 2-(4-(3-methyl-2 butenyloxy) phenoxy group)-1-methylethyl amine (0.86 gram, 3.7 mmole) and pyridine (0.64 the gram, 8.0 also be added dropwise to 2 milliliters of diethyl ether solutions (joining day was above 10 minutes) of Vinyl chloroformate (0.43 gram, 4.0 mmoles) in 8 milliliters of diethyl ether solutions mmole).Mix liquid 1 hour at 5 ℃, then mixed solution is heated to room temperature.Water makes excessive Vinyl chloroformate quenching, and reaction mixture is injected water and ether, with ether (3X) aqueous phase extracted.Mix organic layer with the washing of 2N ammonium sulfate earlier, wash with 10% yellow soda ash then, wash with water again, wash with salt at last to neutrality.With the organic layer drying, filter, remove and desolvate, use the preparative thin layer chromatography purified product, thereby make ethyl n-{ 2-(4-(3-methyl-2-butene oxygen base) phenoxy group)-1-methylethyl } carbamate compounds, its m/s(M
+) see Table Compound C-1 among the C for 307()
Example 2:O-2-(4-(1-methyl propoxy-) phenoxy group)-ethyl n-ethyl thiocarbamate (method b)
With 0.15 gram, 6.0 the sodium hydride of mmole washs with pentane in advance, be dissolved in 5 milliliters of DMF(dimethyl formamides) in, and in ice bath, cool off, add 2-(4-(1-methyl propoxy-) phenoxy group then)-5 milliliters of DMF solution of ethanol (1.26 gram, 6.0 mmoles), under 5 ℃ temperature, mixed liquid 20 minutes, be heated to 50 ℃ then, be 20 minutes heat-up time.Mixed solution is chilled to 5 ℃ again, adds ethyl mustard oil (0.58 milliliter, 6.0 mmoles) and 5 milliliters of DMF, under 5 ℃ temperature, place after 1 hour, mixed solution is heated to room temperature, add 2 methyl alcohol to destroy remaining sodium hydride.Reaction mixture is injected water, use the 3N sulfuric acid acidation.With ether (3X) aqueous phase extracted, water successively, sodium bicarbonate with 10%, water and be mixed with machine mutually with the salt water washing, dry also filtration, concentrated filtrate in a vacuum, use the preparative thin layer chromatography purified product, thereby make O-2-(4-(1-methyl propoxy-) phenoxy group)-ethyl n-ethyl thiocarbamate compound (seeing Table the compd A-36 among the A).
Example 3: ethyl n-{ 2-((3-methyl-2-butene oxygen base) phenoxy group) ethyl } carbamate (method c).
Under 85 ℃ temperature, the 4-(3-methyl-2-butene oxygen base of heating in 20 milliliters of dimethyl formamides (DMF)) phenol (1.64 grams, 9.2 mmole), ethyl 2-chloroethyl amino manthanoate (1.81 grams, 11.9 mmole) and salt of wormwood (2.54 the gram, 18.4 mixture mmole), be 18 hours heat-up time.Reaction mixture is chilled to room temperature, then mixed solution is injected water, use extracted with diethyl ether.Ether hybrid extraction liquid is washed with water to neutrality, with the salt washing, be placed on the calcium sulfate dry then again.Remove in a vacuum and desolvate, place 80 ℃ following 2 hours of high vacuum to remove excessive ethyl 2-chloroethyl amino manthanoate resistates.Use the preparative thin layer chromatography purified product, thereby make ethyl n-{ 2-(4-(3-methyl-2-butene oxygen base) phenoxy group) ethyl } carboxylamine compound (seeing Table compd A among the A-1).Nmr CDcl
3=1.23(t, J=6hz, 3H ,-OCH
2CH
3), 1.77(m, 6H, vinyl methyl), the center is (methylene radical is near NH for m, 2H) at 3.5 places, 4.03(m, 4H, methylene radical is near 0), 4.39(d, J=7H
22H, vinyl methylene radical), the center is at 5.25(bln, 2H, NH and vinyl proton) and 6,8(S, 4H, aromatics proton) PPm.
Example 4: ethyl n-2-(4-(1-methyl propoxy-) phenoxy group) and ethyl } carbamate (method d)
At room temperature, in the DMF of 5 milliliters tetrahydrofuran (THF)s (THF) and 5 milliliters through washed sodium hydride (0.106 gram in advance, 4.4 be added in 5 milliliters of ethyl n-(2-(4-hydroxyl-phenoxy group) ethyl) carbamates (1.0 grams, 4.4 mmoles) in the tetrahydrofuran (THF) mmole).At room temperature mix flood 1.5 hours, and be cooled to-5 ℃ then, in mixture, add 2 milliliters of tetrahydrofuran solutions of 1-methyl-propyl bromide (0.72 gram, 5.3 mmoles), then add 5 milliliters of DMF.Reaction mixture slowly is heated to room temperature, then 60 ℃ of heating 18 hours.Reactant is chilled to room temperature, reactant is injected water, with ether (3X) extractive reaction mixture.Water is washed till neutrality with the ether mixolimnion, then with the salt washing, is placed on above the calcium sulfate dry.Remove in a vacuum and desolvate, use the preparative thin layer chromatography purified product, (see Table compd A among the A-B) thereby make ethyl n-{ 2-(4-(1-methyl propoxy-) phenoxy group) ethyl } carbamate compounds.NmY(CDcl
3)=center is at 0.93 place (m, 3H, CH
3CH
2CH(CH
3)-O), the center is at 1.23 places (t and d, bH, CH
3CH
2CH(CH
3)-O-and OCH
2CH
3), the center is at 1.56 places (m, 2H, CH
3CH
2CH(CH
3)-O-), the center is (m, 2H, the contiguous NH-of methylene radical) at 3.47 places, and the center is (m, 5H, methylene radical and methyne vicinity-O-) at 4.03 places, and (NH), the center is (S, 4H, aromatics proton) PPm at 6.77 places for bm, l at 5.07 places at the center.
Example 5:S-ethyl n-2-(4-(1-methyl-propyl sulfo-) phenyl sulfo-)-ethyl } dithiocarbamate (method e).
N-(4-(1-methyl-propyl sulfo-) phenyl thio-ethyl with 10.0 mmoles)-sylvite of dithiocarbamic acid is dissolved in 30 milliliters of dimethyl formamides, then at N
2Add iodoethane (1 milliliter, 12.5 mmoles) in the atmosphere, stir while adding, at room temperature mix liquid and spend the night.Add the water wiring solution-forming then, use extracted with diethyl ether.Use 10% sulfuric acid successively, water and wash ether layer with salt carries out drying then, removes and desolvates, use the column chromatography purified product, thereby make S-ethyl n-{ 2-(4-(1-methyl-propyl sulfo-) phenyl sulfo-)-ethyl } dithiocarbamate (seeing Table compd A among the A-68).
With method a, b, c, d, the e of similar example 1-5, in the certain limit of method therefor, (see explanation) and can make and list in Table A, B and C(hereinafter) molecular formula be I, I
a, I
b, I
cAnd/or I
dCompound.
The test example:
Example T-1:
With following method calibrating compd A-12, A-13, A-30 and the contact activity of A-36 for housefly.
Wait that with 1 microlitre the acetone soln of examining and determine compound handles the housefly third-instar larvae that moves about after the food respectively with different dose rates.Again equally with 1 another larva of microlitre acetone treatment to compare.Larva was placed lidded container 7 days, and vessel temp is 31 ℃, and the photoperiod is 16 hours.Assay represents that with median effective dose ED50 (this dose unit is a μ g/ larva, promptly required dosage of time spent is made in 50% insects generation to be tested) observed result comprises direct toxicity ((larva death); Delayed toxicity (death of pupa); And juvenile hormone activity, for example, adult can not sprout wings fully, and chitin is suppressed, and epidermis distortion and nymphosis are unusual.The median effective dose ED50 of above-mentioned various compounds to be tested is all less than 0.030 microgram/larva.
Example T-2:
By following method check compd A-1, A-30, A-38 and A-39 activity to the yellow jack mosquito.
The Aedes aegypti four-age larva later stage (dividing wing after common 5 days) is placed in the plastic containers that 50 ml tap waters are housed, be mixed with check compound (concentration is for treating experimental concentration) and 50 microlitre acetone dilute solutions in the water, the hepar siccatum of add-on suspension waterborne is with as food source.Container is added a cover and remained under 28 ℃ of temperature, and the photoperiod is 16 hours, till all larvas or pupa death maybe can not grow up to adult.Assay EC
50Expression, (be medium effective concentration, unit is PPm, and the meaning refers to required concentration of time spent is made in 50% insects generation to be tested).Observed result comprises direct toxicity (larva death) and juvenile hormone activity, can not sprout wings fully as the mortality ratio and the adult of pupa.The EC of above-mentioned compound to be tested
50All less than 0.0010PPm.
Example T-3:
Examine and determine the activity of compd A-13, A-38 and the A-39 of Germany cockroach picked-up with following method.
Compound to be tested (with dose rate to be tested) is sneaked in the dog food to make processed food.100 days third-instar larvaes of blatta germanica nymph are placed in the cage, water and hide are arranged in the cage, weight feed is through the dog food of processing in cage, and compare with unprocessed dog food, cage remained under 28 ℃ the temperature, the photoperiod is 16 hours, and relative humidity is 50%.Normal cockroach adult that grows up of may observe or unusual cockroach adult, normal adult are the long complete normal flat pattern of wing.Also measuring the Reproductive manipulation percentage is 10PPm, and the percent control of reproduction of above-mentioned all cpds is 100%.
Example T-4:
With following method calibrating compd A-1 and A-13 activity to cat flea:
With 1 milliliter of acetone dilute solution of compound to be examined and determine (for experimental concentration) handle glass steel disk (dish of 20mm * 100mm) in slander.Handle the back about about 1 hour, and in each dish, put into the flea developing medium (it contains 50% through disinfectant sand and 50% flea food fine earth) of 1/S teaspoon.Put into the five-age larva (week is big or small) of cat flea in each dish, add a cover on the dish, and under 27 ℃ temperature, placed 35 days under 80% relative humidity.Handle the back number of checking flea adult pupa and larva in 35 days.Test-results is represented with the percentage ratio that suppresses the adult growth, 3.5 * 10
-5Mg/ml or 0.0005 milligram/foot
2Glass surface, the adult growth control rate of above-mentioned all cpds is 100%.
Table A
Molecular formula is that m is l in the compound of I, and m ' is l, and Z is H, CR
1R
2-(CR
3R
4) n is CH
2-CH
2, R
7Be C
2H
5, promptly molecular formula is an I
xCompound:
Compound R W
1W X Y X
1M/e(M
+)
A-1
O O NH O O 293
A-2
O O NH O O 267
A-3 CH≡C-CH
3O O NH O O 263
A-4 CH≡C-CH
2-CH
2-CH
2O O NH O O 291
A-5 Cl-CH＝CH-CH
2O O NH O O 299
A-6
O O NH O O 279
A-7
O O NH O O 347
A-8
O O NH O O 307
＊M
++H
Table A (continuing)
MS
Compound R W
1 1W X Y X
1M/e(M
+)
A-9
O O NH O O 277
+
A-10 CH
2＝CH-CH
2-CH
2-CH
2O O NH O O 293
A-11 CH
3-CH
2-O-CH
2O O NH O O 283
A-12????????O????O????NH????O????O????325
A-13????????O????O????NH????O????O????281
A-14 O O NH O O 296
＊
A-15 Cl-CH
2-CH
2CH
2O O NH O O 301
A-16
O O NH O O 334
A-17
O O NH O O 295
＊M
++H
Table A (continuing)
MS
W
1W X Y X
1m/e（M
+）
O O NH O O 294
＊
O????O????NH????O????O????309
O????O????NH????O????O????295
O O NH O O 310
＊
O????O????NH????O????O????297
O????O????NH????O????O????307
O????O????NH????O????O????307
O????O????NH????O????O????299
O????O????NH????O????O????279
＊M
++H
Table A (continuing)
MS
Compound R W
1W X Y X
1M/e(M
+)
A-27
O O NH O O 309
A-28 CF
3-CH
3O O NH O O 307
A-29
O O NH O O 339
＊＊
A-30
O O O O NH 281
A-31
O O O O NH 293
A-32
O O O O NH
A-33
O O O O NH
A-34
O O O O NH
A-35
O O O O NH
＊＊M
++NH
4
Table A (continuing)
MS
Compound W
1W X Y X
1M/e(M
+)
A-36
O O O S NH 298
＊
A-37
O O O S NH
A-38
S O O S NH 314
＊
A-39
S O O O NH 297
A-40
S O NH O O 297
A-41
S O O S NH
A-42
SS O O O NH 309
A-43
S O NH O O 309
A-44
S S NH O O 313
＊M
++H
Table A (continuing)
MS
Compound W
1W X Y W
1M/e(M
+)
A-45
S S NH O S 330
＊
A-46
S S NH O O
A-47
S S NH O S
A-48
O O NH O S 298
A-49
O O NH O S
A-50
S S NH S NH 328
A-51
O O NH S NH
A-52
S S NH S NH
A-53
O O NH S NH
＊M
++H
Table A (continuing)
MS
Compound W
1W X Y X
1M/e(M
+)
A-54
S S NH O NH 313
＊
A-55
O O NH O NH
A-56
S S NH O NH
A-57
O O NH O NH
A-58
S S O O O 314
A-59
S O O O O 298
A-60
O O O O O 282
A-61
S S O O O
A-62
S O O O O
＊M
++H
Table A (continuing)
MS
Compound W
1W X Y X
1M/e(M
+)
A-63
O O O O O
A-64
S S O O S 330
A-65
O O O O S 298
A-66
S S O O S
A-67
O O O O S
A-68
S S NH S S 346
＊
A-69
O O NH S S
A-70
S S NH S S
A-71
O O NH S S
＊M
++H
Table A (continuing)
MS
Compound W
1W X Y X
1M/e(M
+)
A-72
S S O S S 346
A-73
O O O S S 298
A-74
S S O S S
A-75
O O O S S
A-76
O S NH O O 297
A-77
O S NH O O
A-78
O O NH O O 297
A-79
O O NH O O 297
＊M
++H
Table A (continuing)
MS
Compound W
1W X Y X
1M/e(M
+)
A-82
O O NCH
2O O 295.3
A-83
S O O O S 314
＊
A-84
S O O O S 314
A-85
S O O S S 330
A-86
S O NH S S 330
A-87
O O S O NH 298
＊M
++H
Table A (continuing)
MS
Compound W
1W X Y X
1M/e(M
+)
A-88
S O S O NH 314
A-89
NH O NH O O 293
＊
A-90
（2） O NH O O 361
＊
＊M
++H
（2）N〔CH
2-CH＝C（CH
3）
2〕
Errata
Errata
Claims (10)
1, the preparation molecular formula is the method for the compound of I
In the formula, m and m ' are respectively 0 or 1;
N is 0,1,2 or 3;
R is the alkyl of 1-8 carbon atom, the alkenyl of a 2-8 carbon atom, the alkynyl of a 2-8 carbon atom, the haloalkyl of a 1-8 carbon atom, the halogenated alkenyl of a 2-8 carbon atom, the halo alkynyl of a 2-8 carbon atom, the alkoxyl group alkylthio of a 2-10 carbon atom, the alkyl-thio-alkyl of a 2-10 carbon atom, the cycloalkyl of a 3-8 carbon atom, the halogenated cycloalkyl of a 3-8 carbon atom, cycloalkylalkyl, Heterocyclylalkyl or the Heterocyclylalkyl alkyl of a 4-12 carbon atom;
R
1, R
2, R
3, R
4And R
5Be respectively the alkyl of a hydrogen or 1-8 carbon atom;
R
7Alkyl for 1-8 carbon atom, the alkenyl of 2-8 carbon atom, the alkynyl of 2-8 carbon atom, the haloalkyl of 1-8 carbon atom, the halogenated alkenyl of 2-8 carbon atom, the halo alkynyl of 2-8 carbon atom, the cycloalkyl of 3-8 carbon atom, 4-12 carbon atom cycloalkyl alkyl is 1, be selected from the alkyl of 1-8 carbon atom in 2 or 3 annular carbon atoms, the haloalkyl of 1-8 carbon atom, the alkoxyl group of 1-8 carbon atom, the halogenated alkoxy of 1-8 carbon atom, halogen, nitro, the group of the alkylthio of a cyano group and 1-8 carbon atom replaces or unsubstituted phenyl; When X ' is NR
9The time, R
7Also can be and replace or unsubstituted thio-phenyl and S-C (CH
2)
3-ON group;
R
9For hydrogen or be selected from R
7Group;
W is oxygen, sulphur, NR
5, CR
2R
4Or carbonyl;
W
1Be oxygen, sulphur, NR
8, CR
2R
4, carbonyl, sulfinyl or alkylsulfonyl;
X is oxygen, sulphur or NR
9
X ' is oxygen, sulphur or NR
8
Y is oxygen, sulphur or NR
8And
Z is a hydrogen, the haloalkyl or the halogen of the alkyl of 1-8 carbon atom, a 1-8 carbon atom,
Comprise the steps:
(a) making molecular formula is the compound of II and the reaction of compound that molecular formula is III, and the molecular formula II is:
M, m ', n, R, W ', Z, W, R in the formula
1, R
2, R
3, R
4With the definition of X as above,
The molecular formula III is:
Y, X in the formula
1And R
7Definition as above, Q is a halogen,
(b) making molecular formula is that the compound and the molecular formula of II (definition as above) is the compound of Ia, and molecular formula Ia is:
M, m ', n, R, W ', Z, W, R in the formula
1, R
2, R
3, R
4, X and R
7Definition as above, Y ' is O or S,
The molecular formula IV is:
Y in the formula
1And R
7Definition as above,
(C) making molecular formula is that to make molecular formula be I for the compound of V and the reaction of compound that molecular formula is VI
bCompound, molecular formula I
bFor:
W in the formula
aBe O, S or NR
2, m, n, R, W ', Z, R
1, R
2, R
3, R
4, X, Y, X
1, R
6And R
8Definition as above, molecular formula V is:
M, R, W ', Z and Wa define as above in the formula,
The molecular formula VI is:
N, Q, R in the formula
1, R
2, R
3, R
4, X, Y, X
1And R
7Define as above,
(d) making molecular formula is that to make the molecular formula formula be I for the compound of VII and the reaction of compound that molecular formula is VIII
cCompound, molecular formula I
cFor:
W in the formula
' aBe O, S or NR
3, m ', n, R, Z, W, R
1, R
2, R
3, R
4, X, Y, X
1, R
7And R
8Definition as above, the molecular formula VII is:
M ', n, W in the formula
' a, Z, W, R
1, R
2, R
3, R
4, X, Y, X
1And R
7Define as above, the molecular formula VIII is:
RQ
1
In the formula definition of R as above, Q ' is halogen or methylsulfonyl.
(e) making molecular formula is that to make molecular formula be I for the compound of IX and the reaction of compound that molecular formula is X
bCompound, molecular formula I
dFor:
M, n, R, W ', Z, W, R in the formula
1, R
2, R
3, R
4, X, Y, X
1With the definition of R as above, the molecular formula IX is:
Q in the formula
aBe OM, SM or halogen, M is a kind of basic metal, m, m ', n, R, W ', Z, W, R
1, R
2, R
3, R
4, X and Y definition as above, molecular formula X is:
Q in the formula
bCan be halogen (Q
aBe OM or SM) or can be OM or SM (Q
aBe halogen), R
7Definition as above.
2, the molecular formula by the preparation of the method for claim 1 is the compound of I, and wherein n is 1.
3, the molecular formula by the preparation of the method for claim 2 is the compound of I, and wherein m and m ' are 1.
4, the molecular formula by the preparation of the method for claim 3 is the compound of I, and wherein W ' is O, S or CO, and W is O or S, R ' or R
2Can be the alkyl of a H or 1-5 carbon atom, all the other are H, R
2And R
4Be H, X is the alkyl of O, S, a NH or N(1-5 carbon atom), Y is O or S, R
Be the alkyl of 1-5 carbon atom, the cycloalkyl of a 3-6 carbon atom, the alkenyl of a 3-5 carbon atom, X ' is the alkyl of S, O, a NH or N(1-5 carbon atom).
5, by the method for claim 4, wherein, X can be S or O, and X ' is the alkyl of NH or N(1-5 carbon atom) or K be NH and X
1Be O or S.
6, by the method for claim 5, wherein X can be O or NH.
7, by each the method for claim 1-6, wherein Z is H, and R is the alkyl of 1-5 carbon atom or the alkenyl of 2-5 carbon atom.
8, by the method for claim 7, wherein R is 2-methyl butyl or 3-methyl-2-butene base.
9, the method that is used for controlling insects and mite class comprises: the compound of each defined of claim 1-8 (its consumption with can Pest Control) is applied to insect or it grows the place.
10, a kind of composition of Pest Control is made up of a kind of compound and a kind of thinner of each defined among the claim 1-8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85105807 CN85105807A (en) | 1984-07-18 | 1985-07-30 | The preparation method of novel aromatic compounds |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US63195984A | 1984-07-18 | 1984-07-18 | |
| CN 85105807 CN85105807A (en) | 1984-07-18 | 1985-07-30 | The preparation method of novel aromatic compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN85105807A true CN85105807A (en) | 1987-01-28 |
Family
ID=25741921
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85105807 Pending CN85105807A (en) | 1984-07-18 | 1985-07-30 | The preparation method of novel aromatic compounds |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85105807A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910130A (en) * | 2015-06-23 | 2015-09-16 | 佛山市赛维斯医药科技有限公司 | Xanthate compound containing hexamethylbenzene ring and aminobenzene structures as well as preparation method and application thereof |
| CN104910129A (en) * | 2015-06-23 | 2015-09-16 | 佛山市赛维斯医药科技有限公司 | Xanthate compounds containing hexamethyl benzene ring and halogeno-benzene, and preparation method and application thereof |
-
1985
- 1985-07-30 CN CN 85105807 patent/CN85105807A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910130A (en) * | 2015-06-23 | 2015-09-16 | 佛山市赛维斯医药科技有限公司 | Xanthate compound containing hexamethylbenzene ring and aminobenzene structures as well as preparation method and application thereof |
| CN104910129A (en) * | 2015-06-23 | 2015-09-16 | 佛山市赛维斯医药科技有限公司 | Xanthate compounds containing hexamethyl benzene ring and halogeno-benzene, and preparation method and application thereof |
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