GB1589955A - Cyclopropanecarboxylic acid esters - Google Patents
Cyclopropanecarboxylic acid esters Download PDFInfo
- Publication number
- GB1589955A GB1589955A GB5546/78A GB554678A GB1589955A GB 1589955 A GB1589955 A GB 1589955A GB 5546/78 A GB5546/78 A GB 5546/78A GB 554678 A GB554678 A GB 554678A GB 1589955 A GB1589955 A GB 1589955A
- Authority
- GB
- United Kingdom
- Prior art keywords
- compound
- formula
- larvae
- parts
- test
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
(54) CYCLOPROPANECARBOXYLIC ACID ESTERS
(71) We, CIBA-GEIGY AG, a Swiss body corporate, of Basle, Switzerland,
do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement.
The present invention relates to cyclopropanecarboxylic acid esters, to a process for their manufacture and to their use in pest control.
The cyclopropanecarboxylic acid esters have the formula
wherein R, represents hydrogen, methyl, cyano or ethynyl, X represents chlorine or
bromine, Y represents halogen, methyl or trifluoromethyl.
By halogen is meant fluorine, chlorine, bromine or iodine, especially fluorine or chlorine.
The compounds of the formula I are prepared by methods which are known per se, for example as follows:
X Br 1) ' - Z-CH1O 1) X-C - CH-CH - CH-COOH + Br R1 CH3 CH3 (II) (III) acid accewDbor Y X Br y 2) X-C-CH-CH - CH-COZ + HO-CH > Ot Br C Ci13 CH3 (IV) (V) acid acceptor I I
X Br 3) X-C - CH-CH - CII-COOH + I10-CIltOt C113 C}l R R Cl!3 Cl!3 1 (11) (V) hydrophilic agent X Br y C - C tr - Ci! -CIl-COOR + 4) x - ' =C Br 1 CH3 CH3 (VI) (V) -ROR Y 5) oC=C-CH X C}!COOCl! bromination > x C R C;13 CH3 (VII) In the formulae II, IV, VI and VII, X represents chlorine or bromine and in the formulae III, V and VII, Rl and Y are as defined in formula I.
In the formulae III and IV, Z represents a halogen atom, especially a chlorine or bromine atom, and in formula VI R represents C1 -C4 alkyl, especially methyl or ethyl.
Suitable acid acceptors for processes 1 and 2 are in particular tertiary amines, such as trialkylamine and pyridine, and also hydroxides, oxides, carbonates and bicarbonates of alkali metals and alkaline earth metals, and in addition alkali metal alcoholates, for example potassium tert-butylate and sodium methylate. As hydrophilic agent for process 3, dicyclohexylcarbodiimide can be used for example. Processes 1 to 5 are carried out at a reaction temperature between - 100 and 1200C, usually between 200 and 800C, under normal or elevated pressure and preferably in an inert solvent or diluent. Examples of suitable solvents or diluents are: ether and ethereal compounds, for example diethyl ether dipropyl ether, dioxane, dimethoxy ethane and tetrahydrofurane; amides, such as N,N-dialkylated carboxamides; aliphatic, aromatic and halogenated hydrocarbons, especially benzene, toluene, xylenes, chlorctorm and chlorobenzene; nitriles, such as acetonitrile; dimethyl sulphoxide; and ketones, such as acetone and methyl ethyl ketone.
The starting materials of the formulae II and IV can be prepared by methods known per se e.g. by chlorination or bromination of a compound of the formula:
wherein R2 is hydroxyl or a halogen atom and X represents chlorine or bromine. Starting materials of the formulae III and V to VII are known or can be prepared by methods analogous to known ones.
The compounds of the formula I are in the form of a mixture of different optically 'active isomers if individual optically active starting materials are not used in the reaction. The different isomer mixtures can be separated into the individual isomers by known methods. The compound of the formula I is to be understood as comprising both the individual isomers and the mixtures thereof.
The compounds of the formula I are suitable for controlling a variety of animal and plant pests. In particular, the compounds of the formula I are suitable for controlling insects, phytopathogenic mites and ticks, for example of the orders: Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera, Acarina, Thysanoptera, Orthoptera,
Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera and
Hymenoptera.
In particular, the compounds of the formula I are suitable for controlling insects which are harmful to plants, especially insects which damage plants by eating, in ornamentals and crops of useful plants, especially in cotton plantations (e.g. Spodoptera littoralis and Heliothis virescens) and in vegetable crops (for example Leptinotarsa decemlineata and Myzus persicae).
The active compounds of the formula I also have a very good action against flies, for example Musca domestica and mosquito larvae.
The insecticidal and/or acaricidal action can be substantially broadened and adapted to prevailing circumstances by addition of other insecticides and/or acaricides.
Examples of suitable additives include: organic phosphorous compounds, nitrophenols and derivatives thereof, formamidines, ureas, pyethroids, carbamates, and chlorinated hydrocarbons.
Compounds of the formula I are also combined with particular advantage with substances which exert a synergistic or potentiating effect on pyrethroids. Examples of such compounds include: piperonyl butoxide, propynyl ether, propynyl oximes, propynyl carbamates and propynyl phosphonates, 2-(3,4-methylenedioxyphenoxy)-3,6,9- trioxaundecane (Sesamex or Sesoxane), S,S,S-tributylphosphorotrithioate, 1,2 methylenedioxy-4(2-(octylsulphonyl)-propyl)-benzene.
The compounds of the formula I may be used as pure active substance or together with suitable carriers and/or additives. Suitable carriers and additives can be solid or liquid and correspond to the substances conventionally used in the art of formulation, for example natural or regenerated substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders and/or fertilisers.
The compositions of the present invention are manufactured in known manner by homogeneously mixing and/or grinding active substances of the formula I with the suitable carriers, with or without the addition of dispersants or solvents which are inert to the active substances.
The compounds of the formula I may be processed to the following formulations:
Solid formulations:
Dusts, tracking powders and granules (coated granules, impregnated granules
and homogeneous granules).
Liquid formulations:
a) active substances which are dispersable in water: wettable powders, pastes
and emulsions;
b) solutions.
The content of active substance in the above described compositions is generally between 0.1% and 95%, though concentrations of up to 99.5% or even pure active substance, can also be used if the compositions are applied from an aircraft or other appropriate application devices.
The compounds (active substances) of the formula I can, for example, be formulated as follows (throughout the present specification all parts and percentages are by weight):
Dusts
The following substances are used to produce a) a 5% and b) a 2% dust: a) 5 parts of active substance,
95 parts of talc; b) 2 parts of active substance,
1 part of highly disperse silicic acid,
97 parts of talc.
lhe active substances are mixed with the carriers and ground.
Granules
The following substances are used to produce 5 oX granules:
5 parts of active substance
0.25 parts of epichlorohydrin,
0.25 parts of cetyl polyglycol ether,
3.50 parts of polyethylene glycol,
91 parts of kaolin (particle size 0.3-0.8 mm).
The active substance is mixed with epichlorohydrin and the mixture is dissolved
in 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then
added. The resultant solution is sprayed on kaolin and the acetone is subsequently evaporated in vacuo.
Wettable powders:
The following constituents are used for the preparation of a) a 40%, b) and c) a
25%, and d) a 10% wettable powder: a) 40 parts of active substance,
5 parts of sodium ligninsulphonate,
1 part of sodium dibutylnaphthalenesulphonate,
54 parts parts of silicic acid.
b) 25 parts of active substance,
4.5 parts of calcium ligninsulphonate, 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 1.5 parts of sodium dibutylnaphthaienesulphonate, 19.1 parts of silicic acid,
19.5 parts of Champagne chalk,
28.1 parts of kaolin,
c) 25 parts of active substance,
2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol,
1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1: 8.3 parts of sodium aluminium silicate,
16.5 parts of kieselguhr,
46 parts of kaolin;
d) 10 parts of active substance,
3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates,
5 parts of naphthalenesulphonic acid/formaldehyde condensate,
82 parts of kaolin.
The active substances are homogeneously mixed with the additives in suitable
mixers and the mixture is then ground in appropriate mills and rollers. Wettable
powders are obtained which can be diluted with water to give suspensions of the
desired concentration.
Emulsifiable concentrates:
The following substances are used to produce a) a 10%, b) a 25% and c) a 50%
emulsifiable concentrate:
a) 10 parts of active substance,
3.4 parts of epoxidised vegetable oil,
3.4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ether
and alkylarylsulphonte calcium salt,
40 parts of dimethyl formamide,
43.2 parts of xylene;
b) 25 parts of active substance,
2.5 parts of epoxidised vegetable oil,
10 parts of alkylarylsulphonate/fatty alcohol polyglycol ether mixture,
5 parts of dimethyl formamide,
57.5 parts of xylene;
c) 50 parts of active substance,
4.2 parts of tributylphenol-polyglycol ether,
5.8 parts of calcium dodecylbenzenesulphonate,
20 parts of cyclohexanene,
20 parts of xylene.
By diluting these concentrates with water it is possible to obtain emulsions of the
required concentration.
Sprays:
The following ingredients are used to prepare a) a 5 ,0 spray, and b) a 95% spray:
a) 5 parts of active substance,
1 part of epichlorohydrin,
94 parts of ligroin (boiling range 1600--1900C); b) 95 parts of active substance,
5 parts of epichlorohydrin.
The invention is further illustrated by the following Examples.
Example 1.
Preparation of a-cyano-m-(3-trifluoromethylphenoxy)-benzyl 3-(2',2'-dichloro- 1 ',2 '- dibromoethyl)-2,2-dimethylcyclopropanecarboxylate
14.5 g of Z-cyano-m-(3-trifluoromethylphenoxy)-benzyl 3-(2 ',2 '-dichlorovinyl)- 2,2-dimethylcyclopropanecarboxylate are dissolved in 100 ml of carbon tetrachloride.
To this solution are then added dropwise 4.77 g of Br2 at 200--300C. The reaction mixture is stirred for 2 hours and the carbon tetrachloride distilled off, yielding the compound of the formula
with a refractive index of no,40: 1.5823 (isomer mixture).
The following compounds are also prepared in analogous manner:
C1 Br o I I Cl- c - C!!-CH - c}{-c-O-cri-o / \ C113 CH3 40 l5688 40 (isomer mixture) C1 Br o I I Cl- . ..
Br C - CH-CH - CCINHi & IOH3 CH3 CH3 40 : 1.5689 isomer mixture C1 Br O II + trans Cl-C - CH-CH - CH-C-O-CHtO > CF3 + B1r C1N nod40 : 1.5439 25 CH3 13
C1 Br O I I II Cl-C - CH-CH - Cll-C-0-CHOj Br C CNCl CH3 3 nD :1,5799 + trans C1 Br O I I II Cl-C - CM-C!! - CH-C-0-CH \/ I + cis C Br CN - 40 : 1.5695 6 H3 "D : 1,5695 Cl Br Cl- -/CII-C02CH2-/-7od;" C 1,5809 I I - CH - CH\CoC 2 2 O sO g nD : 1.5809 Br CH3 !! 3 C1 Br Cl- C - CH-CH I F - : 1.5790 I I \o-)--7 20 Br C!!3 C!!3 Cl Br I 1 20 Cl-C - C!! - C!! - C!!-C02C D B1r H20F fl : 1,5810 / \ C!!3 C!!3 C1 Br 39 : 1,5641 Cl- n - H-CH - C!!-C02Cl D I C - CH-CH - CH-C02CH t g) I C CN Br C1I3 C1i3 Cl Br I I C1 - 1.5656 C1-C N L CH3 CH3 Cl Br I I Cl-C - Br - CH - CH-C02CH-/--7 I - CH - CH D : 1.5658 Br /C con C!!3 Cm3 3 ClBr I I Cl Cl-C-C}i-CH /H C 2CH2 - g C1 nD : 1,5854 Brow , C!!3 Cl!3
Example 2.
Insecticidal stomach poison action
Cotton plants were sprayed with a 0.05 aqueous emulsion of active substance (obtained from a 10% emulsifiable concentrate). After the spray coating had dried, the cotton plants were populated with Spodoptera littoralis and Heliothis virescens in the L3-stage. The test was carried out at 240C and 60% relative humidity.
In this test, the compounds of Example 1 exhibited a good insecticidal stomach poison action against Spodoptera and Heliothis larvae.
Example 3.
Action against Chilo suppressalis
Rice seedlings of the variety Caloro were transplanted into plastic pots (6 plants per pot) having a diameter of 17 cm at the top and reared to a height of about 60 cm.
Infestation with Chilo suppressalis larvae (L,-stage, 3 to 4 mm in length) took place two days after the addition of active substance in granule form (rate of application: 8 kg of active ingredient per hectare) to the paddy water. Evaluation of the insecticidal action was made 10 days after addition of the granules. In this test, the compounds of Example 1 acted against Chilo suppressalis.
Example 4.
Acaricidal action
Twelve hours before the test for acaricidal action, Phaseolus vulgaris plants were populated with an infested piece of leaf from a mass culture of Tetranychus urticae.
The mobile stages which had migrated to the plants were sprayed with the emulsified test preparations from a chromatography atomiser in such a way that the spray broth did not run off. The number of living and dead larvae, adults and eggs was evaluated under a stereoscopic microscope after 2 and 7 days and the result expressed in percentage values. During the test run, the plants stood in greenhouse compartments at 250C.
In this test, the compounds of Example 1 acted against adults, larvae and eggs of Tetranychus urticae.
Example 5.
Action against ticks
A) Rhipicephalus bursa
Five adult ticks and 50 tick larvae were counted into each of a number of test tubes and immersed for 1 to 2 minutes in 2 ml of an aqueous emulsion containing a concentration of 100, 10, 1 or 0.1 ppm of test substance. Each test tube was then sealed with a cotton-wool plug and placed on its head to enable the cotton wool to absorb the active substance emulsion. Evaluation of the action against adults was made after 2 weeks and of that against larvae after 2 days. Each test was repeated twice.
B) Boophilus microplus (larvae)
Test were carried out with 20 OP-sensitive and 20 OP-resistant larvae using aqueous emulsions similar to those used in Test A. (The resistance refers to the tolerance towards diazinone). The compounds of Example 1 acted in these tests against adults and larvae of Rhipicephalus bursa and OP-sensitive and OP-resistant larvae of Boophilus microplus.
WHAT WE CLAIM IS:
1. A compound of the formula
wherein R, represents hydrogen, methyl, cyano or ethynyl, X represents chlorine or bromine, and Y represents halogen, methyl or trifluoromethyl.
2. The compound of the formula
3. The compound of the formula
4. The compound of the formula
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (23)
1. A compound of the formula
wherein R, represents hydrogen, methyl, cyano or ethynyl, X represents chlorine or bromine, and Y represents halogen, methyl or trifluoromethyl.
2. The compound of the formula
3. The compound of the formula
4. The compound of the formula
5. The compound of the formula
6. A process for preparing a compound as claimed in claim 1 which process comprises reacting a compound of the formula
(wherein X is as defined in claim 1 and Z represents a halogen atom), in the presence of an acid acceptor, with a compound of the formula
wherein Rl and Y are as defined in claim 1.
7. A process for preparing a compound as claimed in claim 1, which process comprises brominating a compound of the formula
wherein R1, X and Y are as defined in claim 1.
8. A process for preparing a compound as claimed in claim 1 substantially as described herein.
9. A process for preparing a compound as claimed in claim 1 substantially as described in Example 1.
10. A compound according to claim 1 prepared by the process claimed in any one of claims 6 to 9.
11. A pesticidal composition which contains, as active ingredient, a compound as claimed in any one of claims 1 to 5 together with a suitable carrier and/or other ingredient.
12. A composition according to claim 11 which contains the active ingredient together with a solid extender and optionally a surface active agent or together with a liquid diluent and a surface active agent.
13. A method of combating animal or plant pests at a locus which comprises applying to the locus a compound as claimed in any one of claims 1 to 5.
14. A method according to claim 13 wherein the pests are insects or representatives of the order Acarina.
15. A pesticidal composition which contains, as active ingredient, a compound as claimed in any one of claims 1 to 4 together with a suitable carrier and/or other ingredient.
16. A composition according to claim 15 which contains the active ingredient together with a solid extender and optionally a surface active agent or together with a liquid diluent and a surface active agent.
17. A method of combating animal or plant pests at a locus which comprises applying to the locus a compound as claimed in any one of claims 1 to 4.
18. A method according to claim 17 wherein the pests are insects or representatives of the order Acarina.
19. A compounds according to claim 1 wherein Y represents halogen.
20. A pesticidal composition which contains, as active ingredient, a compound as claimed in claim 19 together with a suitable carrier and/or other ingredient.
21. A composition according to claim 20 which contains the active ingredient together with a solid extender and optionally a surface active agent or together with a liquid diluent and a surface active agent.
22. A method of combating animal or plant pests at a locus which comprises applying to the locus a compound as claimed in claim 19.
23. A method according to claim 22 wherein the pests are insects or representatives of the order Acarina.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH169077A CH625396A5 (en) | 1977-02-11 | 1977-02-11 | Pesticides |
| CH934777A CH627921A5 (en) | 1977-07-28 | 1977-07-28 | Pesticides |
| CH18578A CH636074A5 (en) | 1978-01-09 | 1978-01-09 | Cyclopropanecarboxylates, their preparation and use, and pesticides prepared therefrom |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1589955A true GB1589955A (en) | 1981-05-20 |
Family
ID=27171886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB5546/78A Expired GB1589955A (en) | 1977-02-11 | 1978-02-10 | Cyclopropanecarboxylic acid esters |
Country Status (22)
| Country | Link |
|---|---|
| JP (1) | JPS53101341A (en) |
| AU (1) | AU524179B2 (en) |
| BE (1) | BE863838A (en) |
| BG (1) | BG31062A3 (en) |
| BR (1) | BR7800808A (en) |
| CA (1) | CA1132603A (en) |
| DD (1) | DD134720A5 (en) |
| DE (1) | DE2805193A1 (en) |
| EG (1) | EG13058A (en) |
| ES (1) | ES466861A1 (en) |
| FR (1) | FR2380247A1 (en) |
| GB (1) | GB1589955A (en) |
| GR (1) | GR71685B (en) |
| IL (1) | IL54008A0 (en) |
| IT (1) | IT1093629B (en) |
| MX (1) | MX5905E (en) |
| NL (1) | NL7801591A (en) |
| NZ (1) | NZ186449A (en) |
| OA (1) | OA05881A (en) |
| PL (1) | PL111166B1 (en) |
| PT (1) | PT67634B (en) |
| TR (1) | TR20011A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2960827D1 (en) * | 1978-06-27 | 1981-12-03 | Ciba Geigy Ag | Tetrahalogen-ethylcyclopropane carboxylic acid esters, process for their preparation and their use as herbicides |
| PH15324A (en) | 1979-02-27 | 1982-11-18 | Sumitomo Chemical Co | Low mammalian toxic and/or low fish toxic cyclopropanecarboxylate insecticides and/or acaricides |
| FR2469403A1 (en) * | 1979-11-14 | 1981-05-22 | Roussel Uclaf | ESTERS OF HETEROCYCLIC ALCOHOLS, PROCESSES FOR THEIR PREPARATION AND COMPOSITIONS CONTAINING THEM |
| DE3004092A1 (en) * | 1980-02-05 | 1981-08-13 | Bayer Ag, 5090 Leverkusen | SUBSTITUTED 3- (1,2-DIBROM-ALKYL) - 2,2-DIMETHYL-CYCLOPROPAN-1-CARBONIC ACID ESTERS, METHODS AND INTERMEDIATE PRODUCTS FOR THEIR PRODUCTION AND THEIR USE IN PEST CONTROL |
| US4331682A (en) * | 1980-03-14 | 1982-05-25 | Ciba-Geigy Corporation | Cyclopropanecarboxylic acid-α-haloethynyl-m-phenoxybenzyl esters and their use for combating insect pests |
| US4459305A (en) * | 1980-04-10 | 1984-07-10 | Dainippon Sochugiku Kabushiki Kaisha | Cyclopropanecarboxylic acid ester derivatives, a method of manufacturing them, and their uses |
| US4376785A (en) | 1980-06-19 | 1983-03-15 | Sumitomo Chemical Company, Limited | Cyclopropanecarboxylates and a low fish toxic insecticide and/or acaricide containing them |
| FR2512815B1 (en) * | 1981-04-16 | 1989-04-14 | Roussel Uclaf | NOVEL DERIVATIVES OF CYCLOPROPANE CARBOXYLIC ACID, THEIR PREPARATION METHOD, THEIR APPLICATION TO THE CONTROL OF PESTS |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1512955A (en) * | 1974-08-12 | 1978-06-01 | Nat Res Dev | Cyclopropane carboxylic esters |
| DE2706222A1 (en) * | 1976-02-16 | 1977-08-18 | Ciba Geigy Ag | CYCLOPROPANCARBONIC ACID ESTERS, METHOD OF MANUFACTURING AND USING them |
| FR2364884A1 (en) * | 1976-09-21 | 1978-04-14 | Roussel Uclaf | Fungicidal bactericidal cyclopropane carboxylic acid derivs. - are intermediates in prepn. of insecticidal, acaricidal, nematocidal and antifungal ester(s) |
-
1978
- 1978-02-08 DE DE19782805193 patent/DE2805193A1/en not_active Withdrawn
- 1978-02-08 TR TR20011A patent/TR20011A/en unknown
- 1978-02-08 PT PT67634A patent/PT67634B/en unknown
- 1978-02-09 OA OA56402A patent/OA05881A/en unknown
- 1978-02-09 DD DD78203632A patent/DD134720A5/en unknown
- 1978-02-09 GR GR55411A patent/GR71685B/el unknown
- 1978-02-09 IL IL54008A patent/IL54008A0/en unknown
- 1978-02-09 BG BG7838631A patent/BG31062A3/en unknown
- 1978-02-09 FR FR7803673A patent/FR2380247A1/en active Granted
- 1978-02-10 PL PL1978204554A patent/PL111166B1/en unknown
- 1978-02-10 BR BR7800808A patent/BR7800808A/en unknown
- 1978-02-10 BE BE185055A patent/BE863838A/en unknown
- 1978-02-10 CA CA296,701A patent/CA1132603A/en not_active Expired
- 1978-02-10 GB GB5546/78A patent/GB1589955A/en not_active Expired
- 1978-02-10 JP JP1480178A patent/JPS53101341A/en active Pending
- 1978-02-10 IT IT20193/78A patent/IT1093629B/en active
- 1978-02-10 MX MX786839U patent/MX5905E/en unknown
- 1978-02-10 ES ES466861A patent/ES466861A1/en not_active Expired
- 1978-02-10 NL NL7801591A patent/NL7801591A/en not_active Application Discontinuation
- 1978-02-10 AU AU33184/78A patent/AU524179B2/en not_active Expired
- 1978-02-10 NZ NZ186449A patent/NZ186449A/en unknown
- 1978-02-11 EG EG86/78A patent/EG13058A/en active
Also Published As
| Publication number | Publication date |
|---|---|
| FR2380247A1 (en) | 1978-09-08 |
| ES466861A1 (en) | 1979-06-01 |
| BE863838A (en) | 1978-08-10 |
| PT67634A (en) | 1978-03-01 |
| BR7800808A (en) | 1979-01-02 |
| DD134720A5 (en) | 1979-03-21 |
| NL7801591A (en) | 1978-08-15 |
| IL54008A0 (en) | 1978-04-30 |
| GR71685B (en) | 1983-06-21 |
| PL111166B1 (en) | 1980-08-30 |
| EG13058A (en) | 1980-12-31 |
| NZ186449A (en) | 1980-05-27 |
| CA1132603A (en) | 1982-09-28 |
| FR2380247B1 (en) | 1981-04-30 |
| JPS53101341A (en) | 1978-09-04 |
| DE2805193A1 (en) | 1978-08-17 |
| AU3318478A (en) | 1979-08-16 |
| IT7820193A0 (en) | 1978-02-10 |
| IT1093629B (en) | 1985-07-19 |
| AU524179B2 (en) | 1982-09-02 |
| PL204554A1 (en) | 1978-11-06 |
| TR20011A (en) | 1980-06-16 |
| BG31062A3 (en) | 1981-10-15 |
| PT67634B (en) | 1979-07-17 |
| MX5905E (en) | 1984-08-23 |
| OA05881A (en) | 1981-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1095052A (en) | .alpha.,.alpha.-PHENYL-ISOPROPYLACETIC ACID .alpha.-CYANO-3'- PYRIDYL-2'-OXYBENZYL ESTERS | |
| CA1152092A (en) | Pesticidal phenoxybenzyl cyclopropanecarboxylate derivatives | |
| GB1589955A (en) | Cyclopropanecarboxylic acid esters | |
| GB1587352A (en) | Cyclopropanecarboxylic acid esters | |
| US4161536A (en) | Pesticidal aliphatic carboxylates | |
| US4161535A (en) | Pesticidal 2-isopropyl-4-phenyl-3-butenoic acid benzyl esters | |
| US4277494A (en) | Novel esters | |
| CA1156252A (en) | VINYLCYCLOPROPANECARBOXYLIC ACID-3- PHENOXY-.alpha.- VINYLBENZYL ESTERS, PROCESSES FOR PRODUCING THEM, AND THEIR USE IN COMBATING PESTS | |
| US4238504A (en) | Cyclopropanecarboxylic acid-phenoxy-α-vinyl-benzyl esters, processes for producing them, and their use in combating pests | |
| US4336266A (en) | Insecticidal 2,2-dimethyl-3-(2',2'-dihalovinyl)-cyclopropane carboxylic acid 3-halophenoxy-α-vinylbenzyl esters | |
| US4335118A (en) | Insecticidal α-cyano-3-phenoxy-benzyl-2-(4-azidophenyl)-3-methylbutyrates | |
| CA1152093A (en) | Cyclopropane carboxylic acid esters | |
| US4150160A (en) | Pesticidal carbimidocarbonylphenylformamidines | |
| US4221812A (en) | Pesticidal spiropentanecarboxylates | |
| GB2058784A (en) | Dihalovinylcyclopropanecarboxylic acid esters processes for producing them and their use in pest control and also -haloethynyl-3-phenoxy-benzyl alcohols | |
| US4225616A (en) | Tetrahaloethylcyclopropane-carboxylic acid esters | |
| US4264624A (en) | Pesticidal 3-phenoxybenzyl α-cyclopropyl α-phenyl-acetates | |
| US4136106A (en) | 1,3,5-triazapenta-1,4-diene sulfonate esters | |
| US4160843A (en) | Novel amidines | |
| US4316908A (en) | Pesticidal sulfinylamides | |
| US4163056A (en) | Pesticidal triazapentadienes | |
| EP0008331B1 (en) | Cyclopropane carboxylic acid esters, their preparation and use as pesticides | |
| US4115561A (en) | N-phenyl-N'methyl-N"-(O,S-dialkylphosphonyl)-1,3,5-triazapenta-1,4-dienes as pesticides | |
| CH604516A5 (en) | Pyrethroid type insecticides and acaricides | |
| CS208462B2 (en) | Insecticide,acaricide and fungicide means and method of making the active substance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed [section 19, patents act 1949] | ||
| PCNP | Patent ceased through non-payment of renewal fee |