IE41486B1 - Pyridine n-oxide derivatives their manufacture and insecticidal compositions containing them - Google Patents
Pyridine n-oxide derivatives their manufacture and insecticidal compositions containing themInfo
- Publication number
- IE41486B1 IE41486B1 IE1484/75A IE148475A IE41486B1 IE 41486 B1 IE41486 B1 IE 41486B1 IE 1484/75 A IE1484/75 A IE 1484/75A IE 148475 A IE148475 A IE 148475A IE 41486 B1 IE41486 B1 IE 41486B1
- Authority
- IE
- Ireland
- Prior art keywords
- radical
- formula
- compound
- alkyl
- alkoxy
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/89—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/58—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems with hetero atoms directly attached to the ring nitrogen atom
- C07D215/60—N-oxides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pyridine Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Insecticidally active, novel compounds of the formula I in which the symbols R1 to R5 are as defined in Claim 1, which are suitable for the selective control of harmful insects, in particular aphids, are prepared by oxidation of the corresponding pyridines. The oxidation is expediently carried out using oxidants such as hydrogen peroxide or peracids.
Description
This invention relates to pyridine N-oxide derivatives, to a process for their manufacture and to insecticidal compositions containing them.
The present invention provides compounds of the formula
in which one of and Rg is a radical of the formula
and the other is a hydrogen, or halogen atom or a (C^-Cg)alkyl, mono-, di-, or trichloromethyl, trifluoromethyl, (C^-Cg) alkoxy, alkoxycarbonyl, dKC^-C^) alkylaminocarbonyl, phenyl, phenyl (C^-Cg) alkyl or (Cg-Cg) cycloalkyl radical, and 1
R2 is a hydrogen or halogen atom or a (C^-Cg) alkyl, (C^-Cg) alkoxy,(Cg-Cg) cycloalkyl, phenyl(C^-Cg) alkyl, (C^-Cg) alkylcarbonyl, (Cg-Cg)- alkoxycarbonyl, benzoyl, cyano, nitro, di(Cj-Cg)alkylaminocarbonyl or (C^-C^) alkylcarbonylamlno radical; or
R^ and R2 together are a (Cg-Cg) alkylene radical or a radical of the formula
-CH=CH-CH=CH-, and 2Q Rg is a radical of the formula II;
Preferably one of the radicals R and Rg are each a hydrogen or halogen atom or a (C^-C^) alkyl, trifluoromethyl, (Cg-Cg) alkoxycarbonvl, or (Cg-Cg) alkylcarbonyl radical; or Rg and Rg together are a (Cg-Cg) alkylene radical or a radical of the formula
-CH=CH-CH=CH-, which radicals may carry one or more substituents selected from halogen atoms and (Cg-Cg) alkyl, (Cg-Cg)alkoxy, halo (Cg-C2)alkoxy, trifluoromethyl, phenoxy, acetylamino, benzoylamino, nitro, (Cg-Cg)alkoxycarbonyl, mono- and di(Cg-Cg)alkylureido, (Cg-Cg) alkoxycarbonylmethoxy, and di (Cg-Cg) alkylaminooarbonyl radicals; or Rg and Rg together are a radical of the formula and or CIIgOCHg radical.
and Rg represents a dimethylamino carbonyl radical and the other one is a methyl radical or a hydrogen atom. R2 is preferably a hydrogen atom or an acetyl, (Cg-C2)alkoxycarbonyl, or cyano radical, while Rg and Rg together are preferably a tetramethylene or 20 -CH=CH-CH=CH- radical, which radicals are preferably unsubstituted or substituted by fluorine or chlorine atoms or (Cg-Cg)alkyl, (Cg-Cg)-alkoxy, or CFg radicals.
The present invention also provides a process for the manufacture of compounds of the formula 1, which comprises 25 oxidizing compounds of the formula
Suitable oxidizing agents are, besides hydrogen peroxide, peracids, for example performic acid, peracetic acid, halogenated peracetic acids, for example pertrifluoroaoetic acid, perpropionic acid, perlactic acid, monopermaleic acid, mono- . persuocinic acid, perbenzoic acid, substituted perbenzoic acids such as 3-chloroperbenzoic acid, monoperphthalic acid, diperphthalic acid, percamphoric acid, or mixtures thereof. Performic acid, peracetic acid, monopermaleic acid, perbenzoic acid, monoperphthalic acid, 3-chloroperbenzoic acid and hydrogen, peroxide are preferred.
If available, these peracids can be used as such, or they can be prepared in situ, for example by reacting an excess of the basic carboxylic acid or the anhydride thereof with hydrogen peroxide, the excess carboxylic acid or anhydride serving as solvent.
Suitable solvents for hydrogen peroxide or the peraoid are those whioh are inert under the reaction conditions, for example chloroform, dichloroethane,, and chlorobenzene. The oxidising agent is generally used in an amount of from one to several molar equivalents, relative to the starting compound of the formula III. Larger amounts may also be used without disadvantage. The reaction proceeds smoothly at a temperature of from -50°C to 150°C. In general , the reaction is carried out at room temperature or while cooling.
The starting compounds of the formula III can be obtained, for example, by reacting correspondingly substituted 2- or 4hydroxypyridines or quinolines with (a) corresponding carbamoylhalides or (b) phosgene or chloroformic acid esters with subsequent further reaction with a suitable secondary amine (cf. German Offenlegungsschrift No. P 23 61 438). The compounds according to the present invention have considerably higher melting points than the starting compounds of the formula III and, therefore, can be readily separated therefrom, for example by recrystallization.
The compounds of the formula I have a very good selective insecticidal activity, especially against aphids, and also possess excellent systemic properties. They exert their activity not only via the plant foliage but also via the root system. Therefore, aphids living inside plant parts can be combated with good results. The compounds are also active against aphids which have become resistant to phosphoric acid esters.
The present invention therefore also provides insecticidal compositions comprising as active ingredient a compound of the formula I together with one or more formulation additives, and a method of combating insects, especially aphids, which comprises applying to their habitat a compound of the formula 1.
Examples of aphids which can be combated successfully by the compounds of the present invention are Brevlcoryne hrassicae, Myzaphis rosarium, and Aphis schneideri;
Eriosomatidae such as Eriosoma lanigerum; gall-forming aphids such as Pemphigus spec. and Myzodes persicae.
On the other hand, useful coleopters (such as lady birds), butterflies, orthopterae, dipterae, hymenopterae (such as ichneumon flies), and predatory mites feeding on insect pests are not affected even'by high concentrations of the active ingredients. The action on aquatic organisms is insignificant, the compounds having an action on fish only at high concentrations.
The compounds of the present invention and the compositions containing them may be applied In a great variety of ways. They may be applied to the foilage and/or affected parts of the plants or, on the other hand, to the earth surrounding the plant.
Marketable compositions Containing these compounds may be in the form of dusting formulations, powders or granules, the active ingredient being present in admixture with solid extenders or carrier materials such as inert substances
- 6 41486 in powder or granular form. Cer.erally, those compositions contain from 3 - 75$ of these compounds. Suitable solid extenders or carrier materials are, for example, kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talcum, ground magnesia (chalk), fuller's earth .piaster, and diatomaceous or agrillaceoua earths. The compositions may also be used as wettable powders oontaining-in addition to the active ingredient known wetting agents and/or dispersing agents and optionally fillers and/or emulsifiers as further additives.
The compositions may further be used as liquid preparations such as emulsion concentrates for spray liquors which normally contain the active ingredient together with one or several wetting agents, dispersion auxiliaries, or emulsifiers. For liquid preparations organic solvents may also be used. Before application these emulsion conoentrates are normally further diluted to concentrations down to 0.0005$·
The wetting, dispersing and emulsifying agents may be of the cationic, anionic, or non-ionic type.
The oompounds of formula I may also be used as aotive ingredients in fumigants.
The following examples illustrate the invention. PREPARATION EXAMPLES
EXAMPLE 1»
2,6~Dimethyl-4-dimethvlamlnocarbonyloxy-pyrldina-1 oxide
19.4 e (0.1 mole) of 2,6-dlmethyl>4-dimethylaminooarbonyloxy-pyridlne war· dissolved in 150 ml of anhydrous chloroform free of alcohol and, while externally cooling with ioewater and stirring, a solution of 25 8 of 3-chloroperbenzoio acid (70% strength) in 400 ml chloroform was added dropwise.
After standing for 4 days at room temperature the chloroformic solution was shaken three times with 100 ml each of 2H aoda solution and one time with distilled water and the aqueoue extracts were discarded.
After drying of the chloroform phase over calcium ohloride the chloroform was distilled off in vacuo at a bath temperature not exceeding 40°C. The oily residue was crystallized from n-hexane yielding 13,2 g of a product that still contained a small proportion of initial carbamate as ascertained by thin layer chromatography. The crude product was thereforereoryetallized twice from acetonitrile, yielding 5.9 g of a product which was substantially free of initial carbamate and melted at 189 - 190°C ( the initial carbamate melted at 75 76®C).
EXAMPLE 2»
2-Methyl-4-dlmethvlaminooarbonyloxy-quinoline-1 oxide
g (0.1 mole) of 2-methyl-4-dimethylaminooarbonyloxyquinoline were dissolved in 150 ml of dry ohloroform free of aloohol and, while stirring and externally oooling with ice8
41466 water, 25 g 3-ohloroperbenzoi'·- acid (70$ strength) dissolved, in 400 ml chloroform were added dropwise.
After standing for 5 days at room temperature the chlorefortnio solution was shaken three times with 100 ml each of 2N soda solution and one time wi ih. 100 mi distilled water and the aqueous phases were discarded.
After drying over calcium chloride the chloroform was distilled off in a rotary evaporator. The crystalline residue which contained traces of initial carbamate was recrystallized from-n-hexane/toluen
EXAMPLE 3t
2-Methyl-4-dlmethylaTilnocarbonyioxy-5.6,7.8-tetrahydroquinoline oxide
Under the conditions specified in Examples 1 and 2, 18 g (Ο.Ο77 mole) of 2-methyl-4-dimethyl-5»6,7.8-tetrahydroquinoline were oxidized in chloroform with 13.5 g 3-chloroperbenzoio acid (70% strength) .
After removal of chloroform and recrystallization of the residue from n-hexane/benzene, 9.5 g of pure N-oxide melting at 197 - 198°C were obtained. (Melting point of initial carbamate 89°C).
E X A Μ P B
2-Methyl-6-methnxv-4-dimethylaminocarbonyloxygulnoline-1 oxide
33·5 g (0.13 mole) of 2-mothyl-6-meth0xy-4-dimethylamino5 carbonyloxyquinoline were dissolved in 280 ml glacial aoetio acid and 30 ml of a 30$ solution of Hydrogen peroxide were added dropwise at about 0 to 8°C.
After standing for 40 days at room temperature, 2N soda solution was added with, external cooling until the reaotion mixture had a pH of 5· The separating Crystals of the oxidation product were filtered off, washed with cold water and dried, 37 g of crude product were obtained which were freed from traces of initial carbamate by recrystallization, first from ethanol, then from acetonitrile and finally from benzene
8 g of pure N-oxide melting at 172 - 173°θ were finally obtain ed (melting point of initial carbamate 80 - 81°C). EXAMPLE 5l
2-Mothyl-<>-m>thexy-4-dimethylaainocarbonyloxv-5,6 .7,8-tetrahydroquinoline- 1 oxide
·5 C (Ο.Ο96 male) of2-methyl-6-methoxy-4-dimethylaminocarbonyl oxy-5,6,7»8-tetrahydroquinoline were dissolved in 75 ®1 dry, alcohol-free chloroform and oxidized as described in Examples 1 and 2 with a solution of 30 g 3-chloro-perbenzoic acid in
23Ο ml chloroform.
After working up under tho conditions specified in the foregoing examples an oily crude product (31 g) was obtained from which 13 g of crystalline product were obtained by crystallization with n-hexane. Tho product was recrystallized from n-hexane/benzene yielding 6 g of uniform N-oxide melting at 121 - 122°C, (melting point of the starting compound 49 - 51°C).
Tho following N-oxides cf pyridine and mates were prepared in analogous manner1
EXAMPLE structural formula quinoline oarbamelting point
0CON(CHj)j C1- -X \Ach,
I
164 - i66°c
EXAMPLE structural formula melting point
12
1U
OGON(CH,)a
165 - 167°C
165°c
130-131°° structural formula malting point
QCON(CHj)2 ch, l 1
CH, .ι< x(
123 - 124°C
o-c-n(ch3)2 n\ H 4, τ,Η, o J i4o - 150 c 5 18
CH.
115 - 122UC ^So-c-n(ch3)2
O-Q-N(CH )2 χώ,
4» o
·όη3
- 84°C
195 (dacompaaitlon) C
EXAMPLES OF FORMULATION
Example A
A wettable powder readily dispersable in water is obtained by grinding parts by weight of 2-methyl-4-dimethylaminocarbonyloxyquinoline-1 oxide as active ingredient with parts by weight of calcium-magnesium-alumintim silicate and mixing the product obtained with parts by weight of a mixture prepared from parts by weight of cellulose pitch (potassium salt of ligninaulfonic acid) parts by weight of silica (quartz and kaollnite) parts by weight of colloidal silicic acid 7 parts by weight of polypropylene oxide/colloidal silicic acid 1 s 1 part by weight of sodium oleylmethyl taurate.
Example B
An emulsifiable concentrate consists of
1.5 parts by weight of 2-methyI-4-dimethylaminocarbonyloxy5,6,7.8-tetrahydroquinoline-1 oxide
6.5 parts by weight of cyclohexane as solvent and
2.0 parts by weight.of ethoxylated nonyl phenol as emulsifier BIOLOGICAL EXAMPLES
Example I
Potted horse beans (Vicia faba) infested with a stabilized population of bean aphids (Doralis fabae) were sprayed to the drip off with an aqueous dilution of the emulsion concentrate containing the compound of Example 2 as active ingredient in decreasing concentrations. 3 days later the percentage of killed aphids was determined hy counting the surviving and killed animals.
The result is indicated in the following Table I in comparison with two compounds of similar structure and comparable efficiency. The compounds of Example 1 to 6, 8, 10, and 13 to 19 had practically the same efficiency.
- 14 4149«
T able I
Formula # active compound per $ mortality liter spray liquor
c OCONICHg ), Λα, 1 0 0.000375 0.00019 Ο.ΟΟΟΟ95 100 75 ko from Netherlands 0.006 100 Spec. 6,606,695 0.003 98 0.0015 60 OCON(CHS), 0.0006 20
Isolan CHiCHal0·00? 100
An 0.0025 96 (CHaJjj-N-C-O-Zj 0.0012 60 jfCHji 0.0006 20
E x a m ρ 1 e II
The root systems of potted horse beans infested with a population of bean aphids (Doralls fabae) were wrapped in sheets and a glass funnel was inserted into the center of each system. By means of the glass funnels aqueous dilutions of an emulsion concentrate of the compound of Example 2 in decreasing concentration were uniformly distributed in the root area of the test plants. After 8 days the percentage of mortality was determined by counting the dead and surviving aphids on the plants.
mg of active compound 0,5 0.25 0.125 0.06 per root system ......
% mortality 100 100 92 k5
Practically the same results were obtained with the other compounds listed in Example I.
Example III
Populations of Mvzodes persicae on potted paprika plants (Capsicum annum) were sprayed to the drip off with aqueous dilutions of an emulsion concentrate containing the compound of Example 2 in decreasing concentrations. 2 days later the mortality rate was determined by counting the surviving and the dead animals, % active substance per 0.003 0.0015 0.00075 Ο.ΟΟΟ375 liter spray liquor__ % mortalitiy 100 100 92 50
The results obtained with the other compounds listed in Example 1 were practically identical.
Claims (11)
1. CLAIMS:1. A compound of the formula in which one of R| and R 3 is a radical of the formula II / 6 5 -O-C-N I Ry and the other is a hydrogen or halogen atom or a (C|-C 3 ) alkyl, mono-, di-, or trichloromethyl, trifluoromethyl, (C^-Cj) alkoxy, .{C^-C^) alkoxycarbonyl, di(C| - C 4 )alkylaminocarbonyl, phenyl, phenyl (C|-C 3 ) alkyl or (Cg-Cg)-cycloalkyl radical,and 10 R 2 is a hydrogen or halogen atom or a (C|-Cg)alkyl, (C^-Cg) alkoxy, (Cg-Cg)cycloalkyl, phenyl (C^-Cg)alkyl, (C^-Cg) alkylcarbonyl, (C^-Cg)alkoxycarbonyl, benzoyl, cyano, nitro, di(C^-C 3 )alkylaminocarbonyl or (C^-C^)-alkylcarbonylamino radical; or 15 R^ and R 2 together are a (Cg-Cglalkylene radical or a radical of the formula -CH=CH-CH»CH-, and R 3 is a radical of the formula 17 6 -0-C-N \ R. II R^ and Rg are each a hydrogen or halogen atom or a (C^-C^)alkyl, trifluoromethyl, (C^-Cg) alkoxy carbonyl, or (C^-C^alkylcarbonyl radical; or R^ and Rg together are a (Cg-Cg)alkylene radical or a radical of the formula -CH=CH-CH=CH-, which radicals may carry one or more substituents selected from halogen atoms and (C^-C^) alkyl, (C^-Cg)alkoxy, halo-(C^-Cg)alkoxy, CFg, phenoxy, acetylamino, benzoylamino, nitro, (C^-Cg)alkylcarbonyl, monoand di(C 1 -Cg)alkylurido (C^-Cg)alkoxycarbonylmethoxy and dialkylamlnocarbonyl radicals; or R^ and Rg together are a radical Of the formula Rg and Ry are. each a CHg, CgHg, CHgCl, or CHgOCHg radical.
2. The compound
3. ,
4. The compound of the formula - 18 OCON(CH 3 ) 2 41466
5. The compound of the formula
6. The compound of the formula
7. , A process for the manufacture of a compound according to claim 1 which comprises oxidizing a compound of the formula
8. A process according to claim 7 carried out substantially as described in any one of Examples 1 to 19 herein.
9. A compound according to claim 1 whenever manufactured by a process according to claim 7 or claim 8. - 19 41486
10. An insecticidal composition comprising as active ingredient a compound according to claim 1 together with one or more formulation additives.
11. A method of combating insects, especially aphids, which 5 comprises applying to their habitat a compound according to claim 1.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2432635A DE2432635A1 (en) | 1974-07-06 | 1974-07-06 | INSECTICIDAL AGENTS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IE41486L IE41486L (en) | 1976-01-06 |
| IE41486B1 true IE41486B1 (en) | 1980-01-16 |
Family
ID=5919943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE1484/75A IE41486B1 (en) | 1974-07-06 | 1975-07-04 | Pyridine n-oxide derivatives their manufacture and insecticidal compositions containing them |
Country Status (31)
| Country | Link |
|---|---|
| JP (1) | JPS5132736A (en) |
| AT (1) | AT347742B (en) |
| BE (1) | BE831085A (en) |
| BG (1) | BG25194A3 (en) |
| CA (1) | CA1068709A (en) |
| CH (1) | CH609684A5 (en) |
| CS (1) | CS188229B2 (en) |
| DD (1) | DD122774A5 (en) |
| DE (1) | DE2432635A1 (en) |
| DK (1) | DK142198C (en) |
| EG (1) | EG11799A (en) |
| ES (1) | ES439008A1 (en) |
| FI (1) | FI58773C (en) |
| FR (1) | FR2277085A1 (en) |
| GB (1) | GB1454743A (en) |
| HK (1) | HK73878A (en) |
| HU (1) | HU171770B (en) |
| IE (1) | IE41486B1 (en) |
| IN (1) | IN139584B (en) |
| IT (1) | IT1039715B (en) |
| KE (1) | KE2902A (en) |
| LU (1) | LU72905A1 (en) |
| MY (1) | MY7800483A (en) |
| NL (1) | NL7507813A (en) |
| OA (1) | OA05046A (en) |
| RO (1) | RO72908A (en) |
| SE (1) | SE7507707L (en) |
| SU (1) | SU607528A3 (en) |
| TR (1) | TR18212A (en) |
| ZA (1) | ZA754052B (en) |
| ZM (1) | ZM8675A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2570343B2 (en) * | 1987-12-08 | 1997-01-08 | 東ソー株式会社 | Carbamate derivative |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH436834A (en) * | 1965-05-17 | 1966-11-30 | Ciba Geigy | Process for protecting textiles against microorganisms |
-
1974
- 1974-07-06 DE DE2432635A patent/DE2432635A1/en not_active Withdrawn
-
1975
- 1975-06-25 ZA ZA00754052A patent/ZA754052B/en unknown
- 1975-06-25 IN IN1249/CAL/75A patent/IN139584B/en unknown
- 1975-06-30 ES ES439008A patent/ES439008A1/en not_active Expired
- 1975-07-01 NL NL7507813A patent/NL7507813A/en not_active Application Discontinuation
- 1975-07-01 SU SU752150554A patent/SU607528A3/en active
- 1975-07-01 BG BG7500030434A patent/BG25194A3/en unknown
- 1975-07-02 EG EG381/75A patent/EG11799A/en active
- 1975-07-03 OA OA55546A patent/OA05046A/en unknown
- 1975-07-03 CH CH870875A patent/CH609684A5/en not_active IP Right Cessation
- 1975-07-03 FI FI751941A patent/FI58773C/en not_active IP Right Cessation
- 1975-07-04 IE IE1484/75A patent/IE41486B1/en unknown
- 1975-07-04 LU LU72905A patent/LU72905A1/xx unknown
- 1975-07-04 DD DD187101A patent/DD122774A5/xx unknown
- 1975-07-04 IT IT25134/75A patent/IT1039715B/en active
- 1975-07-04 TR TR18212A patent/TR18212A/en unknown
- 1975-07-04 DK DK304075A patent/DK142198C/en active
- 1975-07-04 AT AT515775A patent/AT347742B/en not_active IP Right Cessation
- 1975-07-04 HU HU75HO00001816A patent/HU171770B/en unknown
- 1975-07-04 CA CA230,796A patent/CA1068709A/en not_active Expired
- 1975-07-04 SE SE7507707A patent/SE7507707L/en unknown
- 1975-07-04 ZM ZM86/75A patent/ZM8675A1/en unknown
- 1975-07-04 GB GB2824975A patent/GB1454743A/en not_active Expired
- 1975-07-05 JP JP50082364A patent/JPS5132736A/ja active Pending
- 1975-07-05 RO RO7582756A patent/RO72908A/en unknown
- 1975-07-07 CS CS754810A patent/CS188229B2/en unknown
- 1975-07-07 FR FR7521218A patent/FR2277085A1/en active Granted
- 1975-07-07 BE BE158055A patent/BE831085A/en unknown
-
1978
- 1978-11-15 KE KE2902A patent/KE2902A/en unknown
- 1978-12-14 HK HK738/78A patent/HK73878A/en unknown
- 1978-12-30 MY MY483/78A patent/MY7800483A/en unknown
Also Published As
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO1991007392A1 (en) | Pesticidal pyrimidinyl benzoic acids and esters | |
| KR100229256B1 (en) | Triazole derivatives and insecticides | |
| EP0046467B1 (en) | Quinoxaline derivatives and herbicidal composition | |
| US4041157A (en) | Fungicidal pyrimidine derivatives | |
| US3629474A (en) | Insecticidal and fungicidal compositions and methods of combating fungi and insects using isoxazolyl carbamates | |
| CA1042892A (en) | Hydroxy quinoline carbamates, and their use as insecticides | |
| US4168311A (en) | Hydroxyquinoline carbamates and n-oxide hydroxyquinoline carbamates and their use as insecticides | |
| JP3279818B2 (en) | Insecticide and acaricide | |
| JP2584641B2 (en) | Heterocyclic compounds and herbicides thereof | |
| IE41486B1 (en) | Pyridine n-oxide derivatives their manufacture and insecticidal compositions containing them | |
| JPS63227552A (en) | 2-fluoroethyl derivative, production thereof pest exterminating agent containing said derivative as active ingredient | |
| JPS61103873A (en) | Novel 2-cyanobenzimidazole derivative | |
| JPH07133266A (en) | 3-n-substituted quinazolinone derivative, its production and herbicide containing the same compound | |
| JPS6013039B2 (en) | plant protection agent | |
| JPS6157301B2 (en) | ||
| US4722749A (en) | Pyridinesulfonamides and their use as herbicidal agents | |
| KR100289470B1 (en) | 2-(5-isoxazolinemethyloxyphenyl)-4,5,6,7-tetrahydro-2H-indazole derivatives with herbicidal activity | |
| JPS60233075A (en) | Substituted phenylhydantoin and herbicide containing the same as an active ingredient | |
| US3705914A (en) | Pesticidal carbamate derivatives of naphthaquinones | |
| JPH051060A (en) | 4-thienyl-oxa(thia)zoline derivative and insecticidal miticide containing the same | |
| US3760076A (en) | Combating pests with benzothiadiozines | |
| US3970751A (en) | Certain thiazolotriazolyphosphonothioates used as insecticides | |
| US3551562A (en) | Insecticidal use of s-((4-oxo-1,2,3-benzotriazin - 3(4h)-yl) - methyl) phosphorothioates and phosphorodithioates | |
| US3904639A (en) | Thiazolotriazolyphosphonothioates | |
| JPH045025B2 (en) |