CN1390829A - Diphenylmethanone hydazone derivative and its insecticiding activity - Google Patents
Diphenylmethanone hydazone derivative and its insecticiding activity Download PDFInfo
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- CN1390829A CN1390829A CN 01119493 CN01119493A CN1390829A CN 1390829 A CN1390829 A CN 1390829A CN 01119493 CN01119493 CN 01119493 CN 01119493 A CN01119493 A CN 01119493A CN 1390829 A CN1390829 A CN 1390829A
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Abstract
A diphenylmethanone hydrazone derivative with high insecticiding and miticiding activity is prepared from the condensating reaction between 4,4'-bisubstituted diphenylmethanone, hydrazine hydrate and aldehyde ketone. It can be used for preparing agricultural insecticide.
Description
The present invention relates to the benzophenone hydrazone derivative that a class has good insecticidal action, the biological activity of their preparation method and these compounds.
More existing patents of benzophenone hydrazone derivative and insecticidal activity thereof or technical literature report, these compounds have general structure (I),
According to substituent R
1, R
2, R
3, R
4Form different patent compounds with the different of substituting group number m, n, as U.S. Pat 5,340,837 (structural formula II); US 6,077,866 (structural formula II I); Day disclosure special permission JP 8041013A (structural formula IV); JP 10182625A (structural formula V); JP 10109971A (structural formula VI) etc., these different patent compounds are to the good insecticidal activity of the equal tool of nematode, acarid and mythimna separata, and are generally effective to lepidoptera pest especially, and other organic-biological body and people and animals are then showed harmless or low toxicity.
The present invention is on the basis of existing patent compound, carry out guide's modification, keep the Benzophenonehydrazones basic structure in its molecule, on the hydrazone nitrogen-atoms, introduce alkyl methene structure, and change substituent kind and combination, synthetic obtain the new benzophenone hydrazone derivative of a class, shown in structural formula (VII)
In the structural formula (VII):
X is a halogen, comprises fluorine, chlorine, bromine or iodine, and preferable is chlorine
R
1Be C
1～C
4Alkyl sulphonyl, C
1～C
4Halogenated alkyl sulfonyl, C
1～C
4Alkyl, C
2～C
4Thiazolinyl,
C
1～C
4Haloalkyl or C
2～C
4Haloalkenyl group, preferable is methane sulfonyl or trifluoromethane sulphur
Acyl group
R
2, R
3Be hydrogen, C
1～C
6Alkyl, C
2～C
6Thiazolinyl, C
1～C
6Haloalkyl, C
2～C
6Haloalkenyl group,
Aryl or substituted aryl, or 3～8 yuan of rings, can contain in the ring 1 to 3 identical or different O,
N or S heteroatoms; R
2, R
3Both must not be hydrogen simultaneously; Preferable is R
2, R
3It all is methyl
Or be respectively hydrogen, normal-butyl
R
2, R
3Also can merge into 3～8 yuan of rings, can contain 1 to 3 identical or different O, N or S in the ring
Heteroatoms.
The synthetic of the benzophenone hydrazone derivative that the present invention relates to generally needs four-step reaction, at first, and 4-
Halogeno-benzene formyl chloride and phenol carry out the Fu Ke acylation reaction under the aluminum trichloride (anhydrous) effect in haloalkane solvent such as ethylene dichloride to obtain intermediate (1) be 4-halo-4 '-dihydroxy benaophenonel; Again at tetrahydrofuran (THF), chloroform etc.
Make intermediate (1) and sulfonic acid chloride or halohydrocarbon (YR with pyridine, triethylamine or salt of wormwood etc. as acid binding agent in the solvent
1) to obtain intermediate (2) be 4-halo-4 '-R in reaction
1Oxygen base benzophenone; In the middle of in alcoholic solvent, making then
It is 4-halo-4 '-R that the condensation under small amount of acetic acid catalysis of body (2) and hydrazine hydrate obtains intermediate (3)
1Oxygen base Benzophenonehydrazones; In alcoholic solvent, make intermediate (3) and various aldehyde ketone dehydrating condensation under acetic acid catalysis obtain killing at last
The active target compound benzophenone of worm hydrazone derivative (VII).
By above-mentioned reaction process, change sulfonic acid chloride or halohydrocarbon (YR in second step
1) and four-step reaction in the aldehyde ketone raw material, just can obtain various benzophenone hydrazone derivative by similar reaction and last handling process.
The inventor changes X and substituent R in the molecular structure by molecular designing
1, R
2, R
3And their various combination, synthesized a series of compounds, wherein the part representative compounds is listed in table 1.Prepare required intermediate and final product chemical structure all through mass spectrum and NMR (Nuclear Magnetic Resonance) spectrum conclusive evidence.Table 1
The compounds of this invention is transferred to the living expert of survey and carried out indoor biological activity determination, the object of biological activity determination, method and result: give birth to and survey object: primary dcreening operation worm target is the mite class, mythimna separata, planthopper, aphid.Carry out multiple sieve again after reaching certain biologically active level (＞80%).Sieving target again increases the small cabbage moth and the cotton leaf roller of lepidopterous insects.Give birth to the survey method: [1] mite class: adopt leaf dish spray method (spraying of Potter spray tower).To becoming mite, children if mite and each worm attitude of ovum are carried out biological activity determination.[2] lepidopteran class: adopt and soak the leaf feeding method.Mythimna separata, small cabbage moth and cotton leaf roller are all carried out biological activity determination with 3 instar larvaes.[3] Phytophthira: adopt Potter spray tower spray method.To carrying out biological activity determination as if aphid 2 ages.[4] plant hopper: adopt Potter spray tower spray method.To 3 age nymph carry out biology life and measure.
25 compounds of table 2 are to 4 kinds of target results of preliminary screening
Screening concentration (250mg/L) screening concentration (500mg/L) numbering
( ％ ) ( ％ ) ( ％ ) ( ％ ) ( ％ ) ( ％ ) 1 29.4 57.1 1.1 0.0 0.0 100.02 80.0 95.3 64.0 0.0 45.5 100.03 53.1 66.7 5.4 56.1 89.7 100.04 88.2 27.0 10.9 100.0 64.0 100.05 60.0 23.2 2.2 0.0 61.1 100.06 90.0 20.6 16.3 96.4 75.9 100.07 70.0 76.3 12.0 68.0 22.2 100.08 70.0 5.8 3.3 0.0 0.0 100.09 70.0 4.3 3.3 0.0 0.0 100.010 0.0 2.9 8.7 0.0 0.0 100.011 40.0 24.6 8.7 0.0 0.0 100.012 20.0 15.9 2.2 0.0 0.0 100.013 50.0 23.2 3.3 0.0 0.0 100.014 0.0 26.1 5.4 0.0 0.0 100.015 70.0 78.9 67.0 0.0 100.016 60.0 26.1 13.0 0.0 0.0 0.017 40.0 7.2 1.1 0.0 0.0 100.018 70.0 95.3 6.5 0.0 0.0 0.019 50.0 37.7 6.5 0.0 0.0 100.020 20.0 7.2 2.2 0.0 0.0 100.021 80.0 78.0 2.8 0.0 45.8 0.022 70.0 26.1 0.0 0.0 44.8 100.023 50.0 0.0 0.0 0.0 0.0 100.024 20.0 23.2 0.0 0.0 0.0 100.0：
Results of preliminary screening sees Table 2.Surveying the result as can be seen from giving birth to of table 2, is under the 500mg/L in concentration, except being numbered outside 16,18,21, lepidopterous mythimna separata biological activity is 100% in 25 compounds, has only No. 3 biological activity to reach 89.7% to the paddy rice brown paddy plant hopper; Under 250mg/L, No. 4 and No. 6 biological activitys to aphid are respectively 100% and 96.4%, become mite to be respectively 88.2% and 90.0%, No. 2 and No. 18 to cotton red spider cotton red spider children mite has all been reached 95.3%.
The further multiple sieve of the activated compound of primary dcreening operation is given birth to survey and be the results are shown in table 3.From table 3 data as can be seen, to mythimna separata, be numbered 1,2,3,4,5,7,8,9,19,22 ten its biologically active levels of compound are about 5mg/L, and remaining is more than 20mg/L; To cotton leaf roller, be numbered 1,2,3,4,5,6,7,8,9,22 ten compound biologically active levels are about 50mg/L, and wherein No. 1 compound reaches 10mg/L; To small cabbage moth, number 2,3,5,19,22,23 six compounds concentration be under the 250mg/L biological activity more than 80%; To aphid, have only No. 6 its biological activitys of compound to reach 91.5% under the 50mg/L, rest activity is all lower.
The multiple sieve of table 3 is given birth to and is surveyed the result
Aphid mythimna separata cotton leaf roller small cabbage moth numbering
50mg/L?100mg/L 20mg/L 5mg/L 1mg/L 50mg/L 10mg/L 250mg/L 50mg/L1 100.0 60.0 100.0 93.3 54.5 0.02 100.0 93.3 0.0 100.0 46.7 80.0 0.03 100.0 10.0 100.0 60.0 100.0 50.04 41.2 100.0 15.0 100.0 53.3 72.7 7.75 100.0 0.0 100.0 46.7 100.0 29.06 91.5 100.0 95.0 5.0 100.0 53.3 0.07 100.0 86.7 0.0 100.0 13.3 0.08 100.0 80.0 33.3 100.0 53.3 53.3 0.09 100.0 0.0 100.0 40.0 72.7 0.010 100.0 40.0 0.0 0.011 95.0 5.0 30.0 0.012 100.0 80.0 50.0 5.613 80.0 10.0 6.314 100.0 0.0 0.0 52.4 0.015 80.0 0.0 0.017 100.0 0.0 0.0 5.019 100.0 13.3 40.0 84.6 0.020 70.0 0.0 0.022 100.0 0.0 100.0 26.7 81.8 30.823 100.0?60.0 0.0 90.0 0.024 10.0 0.0 0.0
Synthesis example one, methanesulfonic-4-[(4-chlorophenyl)-(acetone hydrazone fork)-methyl] phenyl ester (compound 1) 1, intermediate 4-chloro-4 '-dihydroxy benaophenonel synthetic
9.4g phenol (0.1mol) is dropped in the 500ml exsiccant there-necked flask, there-necked flask installs thermometer and the cold pipe of ball-type in advance, add 1 of the dry mistake of 250ml, 2-ethylene dichloride stirring and dissolving, weighing drops into 20g aluminum trichloride (anhydrous) (0.15mol) rapidly, oil bath is heated to 70 ℃, beginning slowly drips 17.5g parachlorobenzoyl chloride (0.1mol) by the constant voltage separating funnel, reaction begins immediately, emit a large amount of HCl gases, reactant becomes sorrel, and the control rate of addition keeps temperature of reaction to be no more than 75 ℃, drip off follow-up continuation of insurance temperature 1 hour, till no obvious gas is emitted.Cooling back mixture slowly in the impouring 1000ml frozen water, stirs with glass stick simultaneously and decomposes remaining aluminum chloride, emits HCl gas.Tell organic phase, with 250ml water washing three times, organic phase is spent the night with anhydrous sodium sulfate drying, suction filtration, to get 10.2g yellow particle shape solid with 60ml anhydrous methanol recrystallization be 4-chloro-4 '-dihydroxy benaophenonel to residuum behind the precipitation, 179.5～182 ℃ of fusing points, yield 43.8%.2, intermediate 4-chloro-4 '-methylsulfonyl oxygen benzophenone is synthetic
Get the 1st step synthetic intermediate 4-chloro-4 '-dihydroxy benaophenonel 11.6g (0.05mol), drop in the 150ml single port flask, add 80ml THF, stirring and dissolving.Add 7.04g (0.051mol) triethylamine, Dropwise 5 .85g (0.051mol) methane sulfonyl chloride under the room temperature, stirring reaction 2 hours generates a large amount of white solids.Reheat refluxes to make in 0.5 hour and reacts completely.Cooling, suction filtration concentrate, and it is 4-chloro-4 '-methylsulfonyl oxygen benzophenone that residuum gets 13.6g white powder solid with 50ml dehydrated alcohol recrystallization, 119～121 ℃ of fusing points, yield 87.7%.3, intermediate 4-chloro-4 '-methylsulfonyl oxygen Benzophenonehydrazones is synthetic
Get the 2nd step synthetic intermediate 4-chloro-4 '-methylsulfonyl oxygen benzophenone 7g (22.54mmol), drop in the 250ml single port flask, add the 150ml dehydrated alcohol, adding 4ml 85% hydrazine hydrate (～60mmol), drip 1.5ml acetate, heating reflux reaction 20 hours.Postcooling is finished in reaction, and the decompression precipitation gets white residuum, and with 150ml water agitator treating, suction filtration, getting the 6.2g white solid with the 80ml ethyl alcohol recrystallization again is 4-chloro-4 '-methylsulfonyl oxygen Benzophenonehydrazones, 73～115 ℃ of melting ranges, yield 85%.4, product methanesulfonic-4-[(4-chlorophenyl)-and (acetone hydrazone fork)-methyl] synthetic (compound 1) of phenyl ester
Get the 3rd step synthetic intermediate 4-chloro-4 '-methylsulfonyl oxygen Benzophenonehydrazones 0.5g (1.541mmol), drop in the 50ml single port flask, add the 15ml dehydrated alcohol, add 0.5ml acetone under stirring, drip 0.2ml acetate again, be heated to 55 ℃ of reactions 2.5 hours.Reaction solution is flavescence gradually, and reaction finishes postcooling, separates out yellow solid, suction filtration, obtaining the 0.28g yellow solid with a small amount of cold washing with alcohol is methanesulfonic-4-[(4-chlorophenyl)-(acetone hydrazone fork)-methyl] phenyl ester, 147.5～149 ℃ of fusing points.Synthesis example two, product methanesulfonic-4-[(4-chlorophenyl)-(pimelinketone hydrazone fork)-methyl] synthetic (compound 8) of phenyl ester
Get the 3rd step synthetic intermediate 4-chloro-4 '-methylsulfonyl oxygen Benzophenonehydrazones 0.5g (1.541mmol) in the synthesis example one, drop in the 50ml single port flask, add the 15ml dehydrated alcohol, stir adding 0.196g (2mmol) pimelinketone down, drip 0.2ml acetate again, heating reflux reaction 0.5 hour.The reaction solution flavescence, reaction finishes postcooling, separates out yellow solid, suction filtration, obtaining the 0.52g yellow solid with a small amount of cold washing with alcohol is methanesulfonic-4-[(4-chlorophenyl)-(pimelinketone hydrazone fork)-methyl] phenyl ester.Synthesis example three, product methanesulfonic-4-[(4-chlorophenyl)-(2,4 dichloro benzene formaldehyde hydrazone fork)-methyl] synthetic (compound 15) of phenyl ester
Get the 3rd step synthetic intermediate 4-chloro-4 '-methylsulfonyl oxygen Benzophenonehydrazones 0.5g (1.541mmol) in the synthesis example one, drop in the 50ml single port flask, add the 15ml dehydrated alcohol, stir and add 0.164g (1.541mmol) 2 down, the 4-dichlorobenzaldehyde, drip 0.2ml acetate again, heating reflux reaction 0.5 hour.The reaction solution flavescence, reaction finishes postcooling, separates out yellow solid, suction filtration, obtaining the 0.52g yellow solid with a small amount of cold washing with alcohol is methanesulfonic-4-[(4-chlorophenyl)-(2,4 dichloro benzene formaldehyde hydrazone fork)-methyl] phenyl ester, yield 81%.Synthesis example four, product methanesulfonic-4-[(4-chlorophenyl)-(2 furan carboxyaldehyde hydrazone fork)-methyl] synthetic (compound 22) of phenyl ester
Get the 3rd step synthetic intermediate 4-chloro-4 '-methylsulfonyl oxygen Benzophenonehydrazones 0.5g (1.541mmol) in the synthesis example one, drop in the 50ml single port flask, add the 15ml dehydrated alcohol, stir and add 0.148g (1.541mmol) 2 furan carboxyaldehyde down, drip 0.2ml acetate again, heating reflux reaction 0.5 hour.The reaction solution flavescence, reaction finishes postcooling, separates out yellow solid, suction filtration, obtaining the 0.48g yellow solid with a small amount of cold washing with alcohol is methanesulfonic-4-[(4-chlorophenyl)-(2 furan carboxyaldehyde hydrazone fork)-methyl] phenyl ester, yield 79%.Synthesis example five, product N-[(4-chloro-phenyl-)-(4-p-methoxy-phenyl) methene]-synthetic (compound 21) 1 of N-(2,4 dichloro benzene methene) hydrazine, intermediate 4-chloro-4 '-methoxy benzophenone synthetic
Get the 1st step synthetic intermediate 0.4-chloro-4 '-dihydroxy benaophenonel 5g (2.15mmol) in the synthesis example one, drop in the 50ml single port flask, add 20ml THF, stirring and dissolving, add 0.172g (4.3mol) NaOH, add 0.271g (2.15mmol) methyl-sulfate again, reflux stirring reaction 2 hours, reaction solution gradually becomes white casse by yellow muddiness.Cooling, concentrating under reduced pressure, residuum twice after-filtration of 30ml water agitator treating, it is 4-chloro-4 '-methoxy benzophenone that vacuum-drying gets 0.5g white powder solid.2, intermediate 4-chloro-4 '-methoxy benzophenone hydrazone is synthetic
Get the 1st step of this example synthetic intermediate 4-chloro-4 '-methoxy benzophenone 0.5g (2.03mmol), drop in the 50ml single port flask, add the 20ml dehydrated alcohol, adding 1ml 85% hydrazine hydrate (～20mmol), drip 0.2ml acetate, heating reflux reaction 5 hours.Postcooling is finished in reaction, and the decompression precipitation gets white residuum, with 30ml water agitator treating.Use 30ml chloroform extraction twice again, combining extraction liquid, spend the night with anhydrous sodium sulfate drying in the washing back.It is 4-chloro-4 '-methoxy benzophenone hydrazone that filtering and concentrating gets 0.55g white glass attitude material.3, methene product N-[(4-chloro-phenyl-)-(4-p-methoxy-phenyl)]-N-(2,4 dichloro benzene methene) hydrazine synthetic
Get the 2nd step of this example synthetic intermediate 4-chloro-4 '-methoxy benzophenone hydrazone 0.55g (2.11mmol), drop in the 50ml single port flask, add the 20ml dehydrated alcohol, stir and add 0.369g (2.11mmol) 2 down, the 4-dichlorobenzaldehyde, drip 0.2ml acetate again, heating reflux reaction 0.5 hour.The reaction solution flavescence, reaction finishes postcooling, separates out yellow solid, suction filtration, obtaining the 0.5g yellow solid with a small amount of cold washing with alcohol is the N-[(4-chloro-phenyl-)-(4-p-methoxy-phenyl) methene]-N-(2,4 dichloro benzene methene) hydrazine.
In sum, benzophenone hydrazone compounds molecular structure novelty of the present invention, synthesis material is easy to get, synthetic method is also uncomplicated, biological activity determination shows that most compounds show good desinsection, acaricidal activity, wherein the desinsection biological activity to lepidoptera pest is particularly outstanding, has the value of further research, and being expected to exploitation becomes the agricultural insecticida agent.
Claims (2)
1, a class benzophenone hydrazone derivative is characterized by compound shown in the following structural formula (VII),
In the structural formula (VII):
X is a halogen, comprises fluorine, chlorine, bromine or iodine
R
1Be C
1～C
4Alkyl sulphonyl, C
1～C
4Halogenated alkyl sulfonyl, C
1～C
4Alkyl, C
2～C
4Thiazolinyl,
C
1～C
4Haloalkyl or C
2～C
4Haloalkenyl group
R
2, R
3Be hydrogen, C
1～C
6Alkyl, C
2～C
6Thiazolinyl, C
1～C
6Haloalkyl, C
2～C
6Haloalkenyl group,
Aryl or substituted aryl, or 3～8 yuan of rings, can contain in the ring 1 to 3 identical or different O,
N or S heteroatoms; R
2, R
3Both must not be hydrogen simultaneously
R
2, R
3Also can merge into 3～8 yuan of rings, can contain 1 to 3 identical or different O, N or S in the ring
Heteroatoms.
2, according to the described benzophenone hydrazone derivative of claim 1, it is characterized by the middle X of structural formula (VII) is chlorine; R
1Be methane sulfonyl or trifluoromethane sulfonyl group; R
2, R
3All be methyl or be respectively hydrogen, normal-butyl.
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|---|---|---|---|
| CN 01119493 CN1214001C (en) | 2001-06-07 | 2001-06-07 | Diphenylmethanone hydazone derivative and its insecticiding activity |
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|---|---|---|---|
| CN 01119493 CN1214001C (en) | 2001-06-07 | 2001-06-07 | Diphenylmethanone hydazone derivative and its insecticiding activity |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100387572C (en) * | 2006-06-09 | 2008-05-14 | 浙江工业大学 | Synthetic method for benzophenonehydrazone |
| CN103304553A (en) * | 2013-06-20 | 2013-09-18 | 湖南大学 | 2-(propylene-2-yl)-2,3-dihydro-4-benzofuranol as well as preparation method and application thereof |
| CN105541660A (en) * | 2016-01-15 | 2016-05-04 | 华南理工大学 | Arylsalicylaldehyde-diphenyl-azine hydrazine compound as well as preparation and application |
| RU2785781C1 (en) * | 2022-02-24 | 2022-12-13 | Федеральное государственное автономное образовательное учреждение высшего образования "Пермский государственный национальный исследовательский университет" | Application of 4-(4-bromophenyl)-2-[2-(4-nitrobenzoyl)hydrazono]-4-oxobutanoic acid as an anti-inflammatory drug |
-
2001
- 2001-06-07 CN CN 01119493 patent/CN1214001C/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100387572C (en) * | 2006-06-09 | 2008-05-14 | 浙江工业大学 | Synthetic method for benzophenonehydrazone |
| CN103304553A (en) * | 2013-06-20 | 2013-09-18 | 湖南大学 | 2-(propylene-2-yl)-2,3-dihydro-4-benzofuranol as well as preparation method and application thereof |
| CN105541660A (en) * | 2016-01-15 | 2016-05-04 | 华南理工大学 | Arylsalicylaldehyde-diphenyl-azine hydrazine compound as well as preparation and application |
| CN105541660B (en) * | 2016-01-15 | 2018-01-16 | 华南理工大学 | A kind of aryl salicylide diphenyl azine connection hydrazine class compound and preparation and application |
| RU2785781C1 (en) * | 2022-02-24 | 2022-12-13 | Федеральное государственное автономное образовательное учреждение высшего образования "Пермский государственный национальный исследовательский университет" | Application of 4-(4-bromophenyl)-2-[2-(4-nitrobenzoyl)hydrazono]-4-oxobutanoic acid as an anti-inflammatory drug |
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| Publication number | Publication date |
|---|---|
| CN1214001C (en) | 2005-08-10 |
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