CA1078399A - Insecticidal active thiophene phosphorous derivatives - Google Patents
Insecticidal active thiophene phosphorous derivativesInfo
- Publication number
- CA1078399A CA1078399A CA151,156A CA151156A CA1078399A CA 1078399 A CA1078399 A CA 1078399A CA 151156 A CA151156 A CA 151156A CA 1078399 A CA1078399 A CA 1078399A
- Authority
- CA
- Canada
- Prior art keywords
- thiophene
- carbon atoms
- ethyl
- lower alkyl
- insecticidal active
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/1654—Compounds containing the structure P(=X)n-X-acyl, P(=X)n-X-heteroatom, P(=X)n-X-CN (X = O, S, Se; n = 0, 1)
- C07F9/1657—Compounds containing the structure P(=X)n-X-N (X = O, S, Se; n = 0, 1)
-
- 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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having alternatively specified atoms bound to the phosphorus atom and not covered by a single one of groups A01N57/10, A01N57/18, A01N57/26, A01N57/34
- A01N57/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having alternatively specified atoms bound to the phosphorus atom and not covered by a single one of groups A01N57/10, A01N57/18, A01N57/26, A01N57/34 containing heterocyclic radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/409—Compounds containing the structure P(=X)-X-acyl, P(=X) -X-heteroatom, P(=X)-X-CN (X = O, S, Se)
- C07F9/4096—Compounds containing the structure P(=X)-X-N (X = O, S, Se)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
INSECTICIDAL ACTIVE THIOPHENE
PHOSPHOROUS DERIVATIVES
Abstract of the Disclosure Thiophene phosphorous derivatives and their use as insecticides are described herein. The compounds are defined by the following formula:
PHOSPHOROUS DERIVATIVES
Abstract of the Disclosure Thiophene phosphorous derivatives and their use as insecticides are described herein. The compounds are defined by the following formula:
Description
" .
, , Description of the Invention Th-is invention is directed to a group of compounds which may be generically described as thiophene glyoxylonitrile oxime phosphorous derivatives which are active insecticides.
m e compounds of the present invention are represented S by the general formula C=N-0-~
-C-- N
wherein R is a lower alkyl group having from 1 to 4 carbon atoms - and Rl is selected from lower alkyl and lower alkoxy having from 1 to 4 carbon atoms. The above compounds can be prepared by treating thiophene glyoxylonitrile oxime sodium salt with a dialkyl phosphoryl halide or an alkoxy, alkyl phosphonyl halide. The thiophene glyoxylonitrile oxime sodium salt can be synthesized by treating sodium methoxide with a mixture of thiophene acetonitrile and amyl nitrite in the presence of a solvent.
In order to illustrate the merits of the present inven-tion, the following examples are provided.
Example 1 S,pnthesis of thiophene-2-~lyoxylonitrile oxime sodium salt. ~ 45.3 g. (0.21 moles) of 25% sodium methoxide solution in methanol and 200 ml. of methanol were combined in a 500 ml. three-,~ necked flask fitted with a stirrer, thermometer, dropping funnel and condenser fitted with a calcium chloride drying tube. The solution was stirred and cooled in an ice ~ath at lO~C. A mixture
, , Description of the Invention Th-is invention is directed to a group of compounds which may be generically described as thiophene glyoxylonitrile oxime phosphorous derivatives which are active insecticides.
m e compounds of the present invention are represented S by the general formula C=N-0-~
-C-- N
wherein R is a lower alkyl group having from 1 to 4 carbon atoms - and Rl is selected from lower alkyl and lower alkoxy having from 1 to 4 carbon atoms. The above compounds can be prepared by treating thiophene glyoxylonitrile oxime sodium salt with a dialkyl phosphoryl halide or an alkoxy, alkyl phosphonyl halide. The thiophene glyoxylonitrile oxime sodium salt can be synthesized by treating sodium methoxide with a mixture of thiophene acetonitrile and amyl nitrite in the presence of a solvent.
In order to illustrate the merits of the present inven-tion, the following examples are provided.
Example 1 S,pnthesis of thiophene-2-~lyoxylonitrile oxime sodium salt. ~ 45.3 g. (0.21 moles) of 25% sodium methoxide solution in methanol and 200 ml. of methanol were combined in a 500 ml. three-,~ necked flask fitted with a stirrer, thermometer, dropping funnel and condenser fitted with a calcium chloride drying tube. The solution was stirred and cooled in an ice ~ath at lO~C. A mixture
2 - ~
, . . .
of 2406 g~ (0.21 moles) of isoamylnitrit~_a~d 24.6 g. (0.2 moles) of thiophene-2-acetonitrile was added through the dropping funnel at such a rate that the reaction temperature does not exceed 15C.
After the addition was complete, the ice bath was removed and the reaction mass was stirred for four hours at room temperature.
The reaction mass was then stripped in vacuo of all volatiles.
The residue was titrated with 300 ml. of anhydrous diethylether, and the desired product was collected by filtration.
Example 2 ~ ~-N-0-~ 2 5 8.3 g. (0005 moles) of thiophene-2-glyoxylonitrile oxime sodium salt was dissolved in 150 ml. of acetone in a 250 ml.
flask. Then, 9.4 g. (0.05 moles) of 0,0-diethylthiophosphoryl chloride was added and there was an immediate precipitation of saltO The reaction mass was allowed to stand at room temperature for one hour. Then it was poured into 300 ml. of benzene. The ~S benzene mixture was washed with three 200 ml. portions of wa~er, dried with anhydrous magnesium sulfate, and evaporated in vacuo to yield 13.5 g. (99% of theory) of the desired product.
nD o 105372.
107~399 .. ~ . -, ,: _ Example 3 ~ ~ N ~ CH3 - In a similar manner as set forth in Example 2, 8.2 g.
(0.05 moles) of thiophene-2-glyoxylonitrile oxime sodium salt was combined with 8.2 g. (0.05 moles) of O,O-dimethylthiophosphoryl chloride to produce the desired product. n30 _ 1.5517 Example 4 QLC=N-O-P 2H5 In a similar manner as set forth in Example 2, 8.3 g.
~0.05 moles) of thiophene-2-glyoxylonitrile ox~me sodium salt was combined with 8.6 g. (0.05 moles) of O-ethyl~ethyl thiophosphonyl chloride to produce 12.5 g. of the desired product. n30 _ 1.5665.
Entomolo~ical Testin~ Methods I. House Fly rMusca domestica (L.)]
Ao Film residue A stock solution containing 100 ~g/ml. of the toxicant in an appropriate solvent is prepared. Aliquots of this solution are combined with 1 mlO of an acetone-peanut oil solution in a dish, 55 mm. in diameter, and allowed to dry.
m e aliquots are varied ~o achieve desired toxicant concen-trations ranging fr~m 100 ~g per dish to that at which 50%
. . . .... . . .
- 107839~
,.. ,.. ~ ., . ... ,. ~ . .
mortality is obtained. The dishes are placed in a circular cardboard cage, closed on the bottom with cellophane and covered on top with cloth netting. Twenty-five female house flies are introduced into the cage and the percent mortality is recorded after 48 hours. LD-50 values are expressed in terms of ~% per 25 ~ flies.
II. German Cockroach [Blattella ~ermanica (Linné)l Ten oneqmonth-old nymphs are placed into a circular cardboard cage sealed on one end with cellophane and covered by cloth netting on the other. Aliquots of the toxicant, dissolved in an appropriate solvent, are diluted in water to which has been added 0.0002% of a conventional wetting agent such as polyoxy-ethylene sorbitan mon~laurate ether of alkylated phenols blended with organic sulfonates. Test concentrations range from 0. l~/o to that at which 50% mortality is obtained. Each of these aqueous sus-pensions are sprayed onto the insects, through the cloth netting, by means of a hand spray gun. Percent mortality is recorded after 72 hours and the LD-50 values are expressed as percent of toxicant in the aqueous spray.
III. Saltqmarsh Caterpillar rEsti~mene acrea (Drury)~ , Test solutions are prepared in an identical manner and con-centrations are the same as those for the ~erman cockroach (II).
Sections of bitter dock (Rumex obtusifolius) leaves, 1-1.5 inches in length are immersed in the test solutions for 10-15 seconds and placed on a wire screen to dry. The dried lea~ is placed on a moistened piece of filter paper in a petri dish and infested with five third-instar larvae~ Mortality of the larvae is recorded after 72 hours and the LD~50 values are expressed as percent active ingredient in the aqueous suspensions.
. . .
IV. Black Bean Aphid [Aphis fabae (Scop.)]
Nasturtium (TroPaeolum sp.) plants, approximately 2-3 inches tall, are transplanted into sandy loam soil in 3 inch clay pots and infested with 50-75 aphids of mixed ages. Twenty-four hours later they are sprayed, to the point of runoff, with aqueous suspensions of the toxicant. The suspensions are prepared as in previously described tests (II, III). Test concentrations ranged from 0.05~/0 to that at which 50% mortali~y is obtained. Mortality is recorded after 48 hours and the LD-50 values are expressed as percent active ingredient in the aqueous suspensions.
V. Lygus Bug [LYgus hesperus (Knight)]
iO Same as for the German cockroach (II) except that ~he test concentrations range from 0.05% to that at which 50V/o mortality is obtained.
Vlo Tobacco Budworm [Heliothis virescens (F.)]
Same as for the Salt-marsh caterpillar (III) except that leaves of Romaine lettuce (Latuca sativa~ are utilized as the host plant rather than bitter dock.
VlIo Beet Armyworm [SpodoPtera exi~ua (Hubner)]
Same as the Salt-marsh caterpillar (III) except that leaves of Romaine lettuce (Latuca ~ are utilized as the host plant rather than bitter dock.
VIIIc Mosquito [Culex pipiens quinquefasciates]
100 ml. of an aqueous solution of the test compound, at a ~0 concentration of 0.5 ppm, are placed in a 6 ounce, number 67 Dixie wax paper cup. Ten late third or early fourth instar larvae of the mosquito Culex pipiens quinquefasciates are placed in each ~ 6 -~78399 cup and the cups are stored at 70F. for three days,-at which time mortality counts are made. Compounds which are active at 0.5 ppm are retested at progressively lower concentrations until an LD-50 value is determinedO
TABLE
Compound HF GR SMC BALB TBW Mos BAIJ
Example 1 30 0.02 0.03 0.0080.0008 0.~5 0.03 0.005 Example 2 25 0.08 0.05 0.0080.0008 0.~3 0.008 0.01 Example 3 10 0O005 0.03 0.0030.002 0.05 0.05 0.03 m e compositions of this invention are generally em-bodied into a form suitable for convenient application. For example, the compositions can be embodied into pesticidal formula-tions whîch are provided in the form of em~lsions, suspensions, ~olutions, dusts, and aerosol sprays. In general, such formula-tions will containS in addition to the active compound, the adju-vants which are found normally in pesticide preparations. In these formulations, the active compounds of this invention can be employed as the sole pesticide component or they can be used in admixture with other compounds having similar utility. The pesti-cide formulations of this invention can contain, as adjuvants, organic solvents, such as sesame oil, xylene range solvents, heavy petroleum~ etc., water; emulsifying agents; surface active agents;
talc; pyrophyllite; diatomite; gypsum; clays; propellants, such as dichlorodifluoromethane, etc. If desired, however, the active compositions can be applied directly to feedstuffs, seeds, etc.
upon which the pests feedO Then applied in such a manner, it will be advantageous to use a composition which is not volatile. In connection with the activity of the presently disclosed pesticidal compositionsS it should be fully understood that it is not neces-sary that they be active as suchc The purposes of this invention -- \
.
will be fully served if the composition is rendered active by external influences, such as light, or by some physiological action which occurs when the compound is ingested into the body of the pest.
The precise manner in which the pesticidal compositions of this invention are used in any particular instance will be readily apparent to a person skilled in the art. Generally, the active pesticide composition will be embodied in the form of a liquid composition; for example, an emulsion, suspension, or aerosol spray. While the concentration of the active pesticide composition in the present formulation can vary within rather wide limits, ordinarily, the pesticide composition will comprise not more than about 50.0% by weight of the formulation.
. .
, . . .
of 2406 g~ (0.21 moles) of isoamylnitrit~_a~d 24.6 g. (0.2 moles) of thiophene-2-acetonitrile was added through the dropping funnel at such a rate that the reaction temperature does not exceed 15C.
After the addition was complete, the ice bath was removed and the reaction mass was stirred for four hours at room temperature.
The reaction mass was then stripped in vacuo of all volatiles.
The residue was titrated with 300 ml. of anhydrous diethylether, and the desired product was collected by filtration.
Example 2 ~ ~-N-0-~ 2 5 8.3 g. (0005 moles) of thiophene-2-glyoxylonitrile oxime sodium salt was dissolved in 150 ml. of acetone in a 250 ml.
flask. Then, 9.4 g. (0.05 moles) of 0,0-diethylthiophosphoryl chloride was added and there was an immediate precipitation of saltO The reaction mass was allowed to stand at room temperature for one hour. Then it was poured into 300 ml. of benzene. The ~S benzene mixture was washed with three 200 ml. portions of wa~er, dried with anhydrous magnesium sulfate, and evaporated in vacuo to yield 13.5 g. (99% of theory) of the desired product.
nD o 105372.
107~399 .. ~ . -, ,: _ Example 3 ~ ~ N ~ CH3 - In a similar manner as set forth in Example 2, 8.2 g.
(0.05 moles) of thiophene-2-glyoxylonitrile oxime sodium salt was combined with 8.2 g. (0.05 moles) of O,O-dimethylthiophosphoryl chloride to produce the desired product. n30 _ 1.5517 Example 4 QLC=N-O-P 2H5 In a similar manner as set forth in Example 2, 8.3 g.
~0.05 moles) of thiophene-2-glyoxylonitrile ox~me sodium salt was combined with 8.6 g. (0.05 moles) of O-ethyl~ethyl thiophosphonyl chloride to produce 12.5 g. of the desired product. n30 _ 1.5665.
Entomolo~ical Testin~ Methods I. House Fly rMusca domestica (L.)]
Ao Film residue A stock solution containing 100 ~g/ml. of the toxicant in an appropriate solvent is prepared. Aliquots of this solution are combined with 1 mlO of an acetone-peanut oil solution in a dish, 55 mm. in diameter, and allowed to dry.
m e aliquots are varied ~o achieve desired toxicant concen-trations ranging fr~m 100 ~g per dish to that at which 50%
. . . .... . . .
- 107839~
,.. ,.. ~ ., . ... ,. ~ . .
mortality is obtained. The dishes are placed in a circular cardboard cage, closed on the bottom with cellophane and covered on top with cloth netting. Twenty-five female house flies are introduced into the cage and the percent mortality is recorded after 48 hours. LD-50 values are expressed in terms of ~% per 25 ~ flies.
II. German Cockroach [Blattella ~ermanica (Linné)l Ten oneqmonth-old nymphs are placed into a circular cardboard cage sealed on one end with cellophane and covered by cloth netting on the other. Aliquots of the toxicant, dissolved in an appropriate solvent, are diluted in water to which has been added 0.0002% of a conventional wetting agent such as polyoxy-ethylene sorbitan mon~laurate ether of alkylated phenols blended with organic sulfonates. Test concentrations range from 0. l~/o to that at which 50% mortality is obtained. Each of these aqueous sus-pensions are sprayed onto the insects, through the cloth netting, by means of a hand spray gun. Percent mortality is recorded after 72 hours and the LD-50 values are expressed as percent of toxicant in the aqueous spray.
III. Saltqmarsh Caterpillar rEsti~mene acrea (Drury)~ , Test solutions are prepared in an identical manner and con-centrations are the same as those for the ~erman cockroach (II).
Sections of bitter dock (Rumex obtusifolius) leaves, 1-1.5 inches in length are immersed in the test solutions for 10-15 seconds and placed on a wire screen to dry. The dried lea~ is placed on a moistened piece of filter paper in a petri dish and infested with five third-instar larvae~ Mortality of the larvae is recorded after 72 hours and the LD~50 values are expressed as percent active ingredient in the aqueous suspensions.
. . .
IV. Black Bean Aphid [Aphis fabae (Scop.)]
Nasturtium (TroPaeolum sp.) plants, approximately 2-3 inches tall, are transplanted into sandy loam soil in 3 inch clay pots and infested with 50-75 aphids of mixed ages. Twenty-four hours later they are sprayed, to the point of runoff, with aqueous suspensions of the toxicant. The suspensions are prepared as in previously described tests (II, III). Test concentrations ranged from 0.05~/0 to that at which 50% mortali~y is obtained. Mortality is recorded after 48 hours and the LD-50 values are expressed as percent active ingredient in the aqueous suspensions.
V. Lygus Bug [LYgus hesperus (Knight)]
iO Same as for the German cockroach (II) except that ~he test concentrations range from 0.05% to that at which 50V/o mortality is obtained.
Vlo Tobacco Budworm [Heliothis virescens (F.)]
Same as for the Salt-marsh caterpillar (III) except that leaves of Romaine lettuce (Latuca sativa~ are utilized as the host plant rather than bitter dock.
VlIo Beet Armyworm [SpodoPtera exi~ua (Hubner)]
Same as the Salt-marsh caterpillar (III) except that leaves of Romaine lettuce (Latuca ~ are utilized as the host plant rather than bitter dock.
VIIIc Mosquito [Culex pipiens quinquefasciates]
100 ml. of an aqueous solution of the test compound, at a ~0 concentration of 0.5 ppm, are placed in a 6 ounce, number 67 Dixie wax paper cup. Ten late third or early fourth instar larvae of the mosquito Culex pipiens quinquefasciates are placed in each ~ 6 -~78399 cup and the cups are stored at 70F. for three days,-at which time mortality counts are made. Compounds which are active at 0.5 ppm are retested at progressively lower concentrations until an LD-50 value is determinedO
TABLE
Compound HF GR SMC BALB TBW Mos BAIJ
Example 1 30 0.02 0.03 0.0080.0008 0.~5 0.03 0.005 Example 2 25 0.08 0.05 0.0080.0008 0.~3 0.008 0.01 Example 3 10 0O005 0.03 0.0030.002 0.05 0.05 0.03 m e compositions of this invention are generally em-bodied into a form suitable for convenient application. For example, the compositions can be embodied into pesticidal formula-tions whîch are provided in the form of em~lsions, suspensions, ~olutions, dusts, and aerosol sprays. In general, such formula-tions will containS in addition to the active compound, the adju-vants which are found normally in pesticide preparations. In these formulations, the active compounds of this invention can be employed as the sole pesticide component or they can be used in admixture with other compounds having similar utility. The pesti-cide formulations of this invention can contain, as adjuvants, organic solvents, such as sesame oil, xylene range solvents, heavy petroleum~ etc., water; emulsifying agents; surface active agents;
talc; pyrophyllite; diatomite; gypsum; clays; propellants, such as dichlorodifluoromethane, etc. If desired, however, the active compositions can be applied directly to feedstuffs, seeds, etc.
upon which the pests feedO Then applied in such a manner, it will be advantageous to use a composition which is not volatile. In connection with the activity of the presently disclosed pesticidal compositionsS it should be fully understood that it is not neces-sary that they be active as suchc The purposes of this invention -- \
.
will be fully served if the composition is rendered active by external influences, such as light, or by some physiological action which occurs when the compound is ingested into the body of the pest.
The precise manner in which the pesticidal compositions of this invention are used in any particular instance will be readily apparent to a person skilled in the art. Generally, the active pesticide composition will be embodied in the form of a liquid composition; for example, an emulsion, suspension, or aerosol spray. While the concentration of the active pesticide composition in the present formulation can vary within rather wide limits, ordinarily, the pesticide composition will comprise not more than about 50.0% by weight of the formulation.
. .
Claims (8)
1. Compounds corresponding to the generic formula:
wherein R is a lower alkyl group having from 1 to 4 carbon atoms and R1 is selected from the group of lower alkyl and lower alkoxy having from 1 to 4 carbon atoms.
wherein R is a lower alkyl group having from 1 to 4 carbon atoms and R1 is selected from the group of lower alkyl and lower alkoxy having from 1 to 4 carbon atoms.
2. The compound of Claim 1 wherein R is methyl and R1 is methoxy.
3. The compound of Claim 1 wherein R is ethyl and R1 is ethoxy.
4. The compound of Claim 1 wherein R is ethyl and R1 is ethyl.
5. A method of controlling insects comprising adding to the habitat thereof an effective amount of compounds corres-ponding to the generic formula wherein R is a lower alkyl group having from 1 to 4 carbon atoms and R1 is selected from the group of lower alkyl and lower alkoxy having from 1 to 4 carbon atoms.
6. A method of Claim 5 wherein R is methyl and R1 is methoxy.
7. A method of Claim 5 wherein R is ethyl and R1 is ethoxy.
8. A method of Claim 5 wherein R is ethyl and R1 is ethyl.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US17923371A | 1971-09-09 | 1971-09-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1078399A true CA1078399A (en) | 1980-05-27 |
Family
ID=22655761
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA151,156A Expired CA1078399A (en) | 1971-09-09 | 1972-09-07 | Insecticidal active thiophene phosphorous derivatives |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JPS4836343A (en) |
| AU (1) | AU464309B2 (en) |
| BE (1) | BE788640A (en) |
| BR (1) | BR7206227D0 (en) |
| CA (1) | CA1078399A (en) |
| CH (1) | CH530166A (en) |
| DE (1) | DE2243612A1 (en) |
| FR (1) | FR2152787B1 (en) |
| GB (1) | GB1348218A (en) |
| IL (1) | IL40327A (en) |
| IT (1) | IT967265B (en) |
| NL (1) | NL7212241A (en) |
| ZA (1) | ZA726157B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1086754A (en) * | 1971-12-20 | 1980-09-30 | Robert G. Stein | O-phosphate oximes |
| US3943249A (en) | 1971-12-20 | 1976-03-09 | Abbott Laboratories | O,O-diethylthionophosphonyl-α-oximino-5-chloro-2-thienyl acetonitrile as insecticides |
-
0
- BE BE788640D patent/BE788640A/en unknown
-
1972
- 1972-08-08 GB GB4174072A patent/GB1348218A/en not_active Expired
- 1972-08-25 JP JP47085196A patent/JPS4836343A/ja active Pending
- 1972-09-05 DE DE2243612A patent/DE2243612A1/en active Pending
- 1972-09-07 CA CA151,156A patent/CA1078399A/en not_active Expired
- 1972-09-08 FR FR7231940A patent/FR2152787B1/fr not_active Expired
- 1972-09-08 AU AU46476/72A patent/AU464309B2/en not_active Expired
- 1972-09-08 NL NL7212241A patent/NL7212241A/xx not_active Application Discontinuation
- 1972-09-08 IT IT28956/72A patent/IT967265B/en active
- 1972-09-08 IL IL40327A patent/IL40327A/en unknown
- 1972-09-08 BR BR006227/72A patent/BR7206227D0/en unknown
- 1972-09-08 ZA ZA726157A patent/ZA726157B/en unknown
- 1972-09-11 CH CH1328872A patent/CH530166A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| FR2152787B1 (en) | 1977-08-05 |
| AU4647672A (en) | 1974-03-14 |
| BE788640A (en) | 1973-03-12 |
| IT967265B (en) | 1974-02-28 |
| FR2152787A1 (en) | 1973-04-27 |
| CH530166A (en) | 1972-11-15 |
| GB1348218A (en) | 1974-03-13 |
| IL40327A (en) | 1975-04-25 |
| ZA726157B (en) | 1973-06-27 |
| NL7212241A (en) | 1973-03-13 |
| JPS4836343A (en) | 1973-05-29 |
| IL40327A0 (en) | 1972-11-28 |
| BR7206227D0 (en) | 1973-07-17 |
| AU464309B2 (en) | 1975-08-21 |
| DE2243612A1 (en) | 1973-03-15 |
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