CN1099408C - Biocidal oximido ether compound - Google Patents
Biocidal oximido ether compound Download PDFInfo
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- CN1099408C CN1099408C CN98112665A CN98112665A CN1099408C CN 1099408 C CN1099408 C CN 1099408C CN 98112665 A CN98112665 A CN 98112665A CN 98112665 A CN98112665 A CN 98112665A CN 1099408 C CN1099408 C CN 1099408C
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- formula
- alkyl
- oximinoether
- biocidal
- oxime
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Abstract
The present invention discloses a series of compounds of biocidal oxime ethers showed by a general formula (I) which is disclosed in the specification, and a preparation method thereof. The compound of formula (I) is obtained by the reaction of a formula II and a formula III under the alkaline condition at normal pressure and at the temperature of 20 to 120 DEG C for 3 to 10 hours, wherein organic solvents, such as water, benzene or toluene, etc., and phase transfer catalysts are added. The compounds in the present invention have better bioactivity: some of the compounds display a superior inhibitory activity to magnaporthe grisea, rice sheath blight bacterium, sclerotinia sclerotiorum, rhizoctonia rot of cotton bacterium or fusarium blight bacterium; some of the compounds display a good insecticidal activity to pests, such as armyworm, bean aphid, leaf hopper, etc.; some other compounds display both a certain herbicidal activity and a growth regulating activity.
Description
The present invention relates to a series of biocidal oximinoethers and preparation method thereof.
The research of relevant oxime ether agricultural chemicals, existing both at home and abroad lot of documents report, [P.114 et seq.Cambridge 1990 for G.Holan et al., Recent Advances inthe chemistry of Insect Control II; T.G.Cullen et al., ACSSymp.Ser.335 (1987) 173; M.J.Bull et al., Pestic.Sci.11 (1980) 349; WO-A-84/01772; CN 1077709A.].Also there are simultaneously a plurality of commercially available agricultural chemicals to come out, as oxime ether chrysanthemum ester; LGC-40863 is THE 1997BRIGHTON CROP PROTECTION CONFERENCE VOL1 P39.This compounds has good desinsection, kills mite, sterilization, nematicide and weeding isoreactivity, and characteristics such as efficient, low residue are arranged mostly.Oximinoether obtains developing more widely and using as a kind of novel agrochemical.
The present invention is to provide the oximinoether shown in the general formula I:
R in the general formula I
1And R
2Can be identical or different, represent H, C
1～C
6Alkyl, C
3～C
8Cycloalkyl, aryl or heteroaryl, aryl carbonyl, alkyl-carbonyl, alkyl hydrogen sulfenyl, cyano group; R
1And R
2Also can link together and form an alkylidene chain.In preceding determined implication, in case of necessity, be selected from following identical or different one or more substituting groups and replaced: C
1～C
6Alkyl, C
6～C
12Aryl or C
6～C
12Heteroaryl, halogen, nitro, cyano group, hydroxyl, C
1～C
6Alkyl oxy, C
6～C
12Aryloxy, alkyl hydrogen sulfenyl, aryl thiohydroxy, methylenedioxy group; R represents C in the general formula I
1～C
6Alkyl, C
6～C
12Aryloxy, halogen; X represents C or N in the general formula I.The ether of oxime shown in the general formula I can occur by two kinds of isomeric forms: " Z formula " and " E formula " form promptly connects radicals R on the carbon-to-nitrogen double bon carbon
1And R
2Press the CIP sequence rules and determine position successively, when order the preceding group and oxime-oxygen be in homonymy, be " Z formula ", otherwise, when order after group and oxime-oxygen when being in homonymy, then be " E formula ".
Z formula E formula
Press CIP sequence rules R
1At R
2Compound shown in the preceding general formula I can be Z formula or E formula, also can be both mixtures.
The invention provides the preparation method of compound of Formula I, is with compound reaction shown in compound shown in the formula II and the formula III.
R in formula II and the formula III
1, R
2, X and R be suc as formula defining among the I, Z represents a leavings group.
The preparation method of formula I compound generally is under alkaline condition, exist down as alkali metal hydroxide, alkali metal hydrocarbonate or tertiary amine etc., add entry and organic solvents such as benzene or toluene, add phase-transfer catalyst PTC again, as tetrabutylammonium iodide or Tetrabutyl amonium bromide, promptly got compound shown in the general formula I in 3～10 hours in normal pressure, 20～120 ℃ of conditioned responses.The gained compound of Formula I is separated purification through decompression column chromatography or recrystallization.
During the oxime alkylated reaction, the three-dimensional arrangement of oxime can not change usually, and promptly Z formula oxime obtains Z formula oxime ether, and E formula oxime obtains E formula oxime ether.
Oxime shown in the formula II can by common preparation method by aldehydes or ketones and hydroxylammonium salts example hydrochloric acid azanol or oxammonium sulfate 0～100 ℃ in water or pure equal solvent, also need add appropriate base such as alkali metal hydroxide or alkali metal hydrocarbonate sometimes and synthesize.
The mixture of oxime or isomery oxime can be converted into thermodynamically stable form by methods such as photoisomerization, thermic isomerization and isoversions.
Oximinoether provided by the invention has better biological activity to insect, evil mite class, pathogenic fungi and weeds.When adopting toxic medium therapy to test each compound 100ppm to Pyricularia oryzae, Rhizoctonia solani Kuhn, Sclerotinia sclerotiorum, cotton rhizoctonia solani, fusarium graminearum mycelial growth inhibition rate.Some compound reaches 100% to Pyricularia oryzae, Rhizoctonia solani Kuhn, Sclerotinia sclerotiorum, cotton rhizoctonia solani and fusarium graminearum mycelial growth inhibition rate.The insecticidal activity of each compound adopts several different methods such as spray method, pickling process and topical application to measure.Some compound has shown good insecticidal activity to insects such as mythimna separata, bean aphid, green rice leafhoppers, and when adopting pickling process to handle the green rice leafhopper nymph as the concentration with 500ppm, the 24hr mortality ratio reaches 100%; The 24hr mortality ratio reaches 100% when with the concentration of 1000ppm mythimna separata 3 instar larvaes being sprayed processing.In addition, some compound also has certain weeding activity simultaneously, and individual compound has the plant growth of promotion effect.
The invention will be further described below in conjunction with embodiment.Embodiment 1:1, synthetic (the example 105 routine compounds in the table 1) of 2,4 triazolyl methyl tertiary butyl ketoximes-O-6-chloro-3-pyridyl methyl ether
Get 2.19 gram (0.012 moles) 1,2,4-triazolyl methyl tertiary butyl ketoxime (123.6～123.8 ℃ of fusing points) places reaction flask, add 1.01 gram sodium hydroxide, 15 ml waters, 5 milliliters of toluene, 0.5 gram Tetrabutyl amonium bromide, 2.04 gram (0.012 mole), mole, 95%) 6-chloro-3-chloromethylpyridine, 62 ℃ of left and right sides stirring reactions 7～8 hours, after the cooling, use the methylbenzene extraction organic layer, the washing organic layer is to neutral, slough toluene, there is the solid thing of yellow particle shape to separate out, after the salt water washing 2～3 times, must yellow crystals with sherwood oil and acetone recrystallization 2～3 times.Naturally oven dry gets product 2.78 grams.98.1～98.7 ℃ of fusing points, productive rate 75.3%.
Results of elemental analyses (actual measurement/calculating) C%:54.69/54.63 H%:5.79/5.89 N%:22.40/22.75
Hydrogen spectrum δ
CDCl3TMS 1.16 (s, 9H, C (CH
3)
3), 4.94 (s, 2H, 1,2,4-triazolyl-CH
2-C=NO), 5.08 (s, 2H, C=NOCH
2), 7.26～8.38 (m, 5H, hydrogen on the heterocycle)
INFRARED SPECTRUM 1566cm
-1And 1591cm
-1Be the two spectrum of the feature peak that C=C and C=N stretching vibration cause in the pyridine ring, 3051cm
-1Be C-H stretching vibration on the pyridine ring, 1361cm
-1, 1394cm
-1And 1462cm
-1Be C-H symmetry and asymmetrical deformation vibration characteristic peak in the tertiary butyl.Embodiment 2:1,2, synthetic (intermediate of embodiment 1 is synthetic) of 4-triazolyl methyl tertiary butyl ketoxime
In 500 milliliters of there-necked flasks that reflux condensing tube is housed, add 1,2,4-triazolyl methyl tertiary butyl ketone 151 grams (36% aqueous solution, about 0.32 mole), 120 milliliters of ethanol, oxammonium hydrochloride 41.6 grams (about 0.6 mole) add 35.7 gram sodium bicarbonates more in batches, finish, reflux 10～12 hours, cooling gets crystallization, and the frozen water washing for several times, suction filtration is dried to such an extent that product 51 restrains naturally.123.6～123.8 ℃ of fusing points, yield 87.9%.
All oxime ether and oxime can be synthetic with similar method, and institute's synthetic compound all through hydrogen spectrum, infrared conclusive evidence, also prove conclusively through ultimate analysis simultaneously by majority of compounds.Other compounds see Table 1.
The implication of symbology shown in the table 1 is as follows: E
1---------------4-tert-butyl-phenyl E
2---------------4-chloro-phenyl-E
3---------------3-Phenoxyphenyl E
4---------------6-chloro-pyridine-3-base Me---------------methyl Et---------------ethyl n-Pr---------------n-propyl i-Pr---------------sec.-propyl Bu---------------butyl t-Bu---------------tertiary butyl ph---------------phenyl
Table 1 oxime ether series compound
Claims (5)
1. biocidal oximinoether is characterized in that: a series of compounds shown in the general formula I are provided.
R in the general formula I
1And R
2Can be identical or different, represent H, C
1～C
6Alkyl, C
3～C
8Cycloalkyl, aryl or heteroaryl, aryl carbonyl, alkyl-carbonyl, alkyl hydrogen sulfenyl, cyano group; R
1And R
2Also can link together and form an alkylidene chain; In preceding determined implication, in case of necessity, also can be selected from following identical or different one or more substituting groups and replace: C
1～C
6Alkyl, C
6～C
12Aryl or C
6～C
12Heteroaryl, halogen, nitro, cyano group, hydroxyl, C
1～C
6Alkyl oxy, C
6～C
12Aryloxy, alkyl hydrogen sulfenyl, aryl thiohydroxy, methylenedioxy group; R represents C in the general formula I
1～C
6Alkyl, C
6～C
12Aryloxy, halogen; X represents C or N in the general formula I.
2. according to the described biocidal oximinoether of claim 1, it is characterized in that: oxime ether compound (I) can be Z formula or E formula, also can be both mixtures; Connect basic R on the carbon-to-nitrogen double bon
1And R
2Press the CIP sequence rules and determine position successively, when order the preceding group be in homonymy with oxime-oxygen, then be the Z formula, otherwise, order after group and oxime-oxygen to be in homonymy then be the E formula.
Z formula E formula
Press CIP sequence rules R
1At R
2Before
3. according to the described oximinoether of claim 1, it is characterized in that insect, evil mite class, pathogenic fungi and weeds are had biological activity.
4. according to the preparation method of claim 1 or 2 described biocidal oximinoethers, it is characterized in that: use compound shown in the formula II and the compound shown in the formula III in the presence of alkali, add entry and benzene or toluene organic solvent, add phase-transfer catalyst PTC again, under normal pressure, 20～120 ℃ of conditions, reacted 3～10 hours and get R in the formula
1, R
2, X is identical with the definition among the formula I with R, Z represents a leavings group.
5. according to the preparation method of the described biocidal oximinoether of claim 4, it is characterized in that preparing the used alkali of oximinoether is alkali metal hydroxide, alkali metal hydrocarbonate or tertiary amine; Phase-transfer catalyst PTC is tetrabutylammonium iodide or Tetrabutyl amonium bromide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98112665A CN1099408C (en) | 1998-10-07 | 1998-10-07 | Biocidal oximido ether compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98112665A CN1099408C (en) | 1998-10-07 | 1998-10-07 | Biocidal oximido ether compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1250046A CN1250046A (en) | 2000-04-12 |
| CN1099408C true CN1099408C (en) | 2003-01-22 |
Family
ID=5222492
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98112665A Expired - Lifetime CN1099408C (en) | 1998-10-07 | 1998-10-07 | Biocidal oximido ether compound |
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Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100579956C (en) * | 2003-12-12 | 2010-01-13 | 湖南化工研究院 | Insecticidal antibacterial sulphur, oxygen and oxime-containing ether compounds |
| TW200634000A (en) * | 2004-12-22 | 2006-10-01 | Shionogi & Co | 2-(pyrazol-1-yl)pyridine derivatives |
| CN101037397B (en) * | 2006-03-17 | 2010-05-12 | 湖南化工研究院 | Purification method of non-fatty oxime ether pyrethrin compound |
| CN102030680B (en) * | 2010-10-20 | 2014-03-26 | 湖北省生物农药工程研究中心 | Novel oxime ether or ester derivatives with insecticidal activity |
| CN102229573B (en) * | 2011-05-03 | 2013-03-13 | 湖南大学 | 1-(1,2,4-triazole-1-group)ketoxime ethers and its application in preparation of bactericide |
| CN102260219B (en) * | 2011-06-10 | 2013-06-12 | 湖南大学 | 1-(1,2,4-triazolyl)ketoxime ether-acylamide and application thereof |
| CN104803929B (en) * | 2014-01-28 | 2017-11-14 | 沈阳中化农药化工研发有限公司 | A kind of substituted oximinoether kind compound and application thereof |
| CN110015977B (en) | 2015-12-25 | 2020-09-15 | 沈阳中化农药化工研发有限公司 | Malononitrile oxime ether compound and its use |
| CN108440338A (en) * | 2018-04-26 | 2018-08-24 | 江西农业大学 | The synthesis and its application of laurine oxime and its alkyl ether |
| CN112189663B (en) * | 2019-07-08 | 2022-03-22 | 沈阳中化农药化工研发有限公司 | Fungicidal and bacterial composition and application |
| CN112189669B (en) * | 2019-07-08 | 2022-03-08 | 沈阳中化农药化工研发有限公司 | Fungicidal and bacterial compositions and uses |
| CN112189660B (en) * | 2019-07-08 | 2022-03-08 | 沈阳中化农药化工研发有限公司 | Fungicidal and bacterial compositions and uses thereof |
| CN112189665B (en) * | 2019-07-08 | 2022-03-22 | 沈阳中化农药化工研发有限公司 | Fungicidal bacterium composition and application |
| CN112189662B (en) * | 2019-07-08 | 2022-03-08 | 沈阳中化农药化工研发有限公司 | Fungicidal and bacterial compositions and uses thereof |
| CN112189661B (en) * | 2019-07-08 | 2022-03-29 | 沈阳中化农药化工研发有限公司 | Fungicidal and bacterial compositions and uses |
| CN112189668B (en) * | 2019-07-08 | 2022-03-08 | 沈阳中化农药化工研发有限公司 | Fungicidal and bacterial composition and application |
| CN114532346B (en) * | 2020-11-19 | 2023-07-07 | 沈阳中化农药化工研发有限公司 | Fungicidal and bacterial composition and application thereof |
| CN113429313B (en) * | 2021-06-09 | 2022-07-12 | 浙江锦华新材料股份有限公司 | Preparation method of acetone oxime methyl ether |
| CN114591197A (en) * | 2022-03-01 | 2022-06-07 | 浙江圣安化工股份有限公司 | Process method for continuously synthesizing oxime ether |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1109686A (en) * | 1993-05-18 | 1995-10-04 | 希巴-盖吉股份公司 | O-benzyl oxime ether derivatives and their use as pesticides |
-
1998
- 1998-10-07 CN CN98112665A patent/CN1099408C/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1109686A (en) * | 1993-05-18 | 1995-10-04 | 希巴-盖吉股份公司 | O-benzyl oxime ether derivatives and their use as pesticides |
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|---|---|
| CN1250046A (en) | 2000-04-12 |
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