GB1591282A - Phosphorus-containing thiosubstituted carbamic acid derivatives - Google Patents

Phosphorus-containing thiosubstituted carbamic acid derivatives Download PDF

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Publication number
GB1591282A
GB1591282A GB47923/77A GB4792377A GB1591282A GB 1591282 A GB1591282 A GB 1591282A GB 47923/77 A GB47923/77 A GB 47923/77A GB 4792377 A GB4792377 A GB 4792377A GB 1591282 A GB1591282 A GB 1591282A
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compound
formula
methyl
plants
test
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Novartis AG
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Ciba Geigy AG
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Priority claimed from CH1452576A external-priority patent/CH627621A5/en
Priority claimed from CH678877A external-priority patent/CH633681A5/en
Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Publication of GB1591282A publication Critical patent/GB1591282A/en
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    • 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
    • A01N57/26—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-nitrogen bonds
    • 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
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/2479—Compounds containing the structure P(=X)n-N-acyl, P(=X)n-N-heteroatom, P(=X)n-N-CN (X = O, S, Se; n = 0, 1)
    • C07F9/2483—Compounds containing the structure P(=X)n-N-acyl, P(=X)n-N-heteroatom, P(=X)n-N-CN (X = O, S, Se; n = 0, 1) containing the structure P(=X)n-N-S (X = O, S, Se; n = 0, 1)

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Molecular Biology (AREA)
  • Biochemistry (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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)

Description

(54) PHOSPHORUS-CONTAINING THIOSUBSTITUTED CARBAMIC ACID DERIVATIVES (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 novel phosphorus-containing thiosubstituted carbamic acid derivatives which act against insect, to a process for their manufacture and to insecticidal compositions which contain these derivatives as active ingredient, and to a method of combating insects which comprises the use of the novel compounds.
The thiosubstituted carbamic acid derivatives of the present invention have the formula
wherein R1 and R2, each independently of the other, is method, ethoxy or dimethylamino, R3 is C1-C8 alkyl, C3-C6 cycloalkyl or cyclopropylmethyl, R4 is methyl or ethyl and R5 is C1-C5 alkyl.
Alkyl groups represented by R3 and R5 can be branched or straight-chain.
Such groups can be for example the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec- and tert-butyl group, as well as the n-pentyl group and isomers thereof, and in the case of R3 the n-hexyl and n-octyl groups and the isomers thereof. By C3-C6 cycloalkyl is meant for example cyclopropyl, cyclopentyl and cyclohexyl.
In the compounds of the formula I, the following substituents and combinations thereof are preferred: i) for R1 and R2: methoxy and ethoxy; ii) for R3: C1-C4 alkyl, cyclopropyl, cyclohexyl and cyclopropylmethyl, in particular methyl, ethyl and cyclopropyl, especially methyl or ethyl; iii) for R4: methyl; and iv) for R5: methyl and ethyl.
Accordingly, the following compound subgroups are for example preferred: i) compounds of the formula I wherein R1 and R2, each independently of the other, is methoxy or ethoxy, R3 is C1-C4 alkyl, cyclopropyl, cyclohexyl or cyclopropylmethyl, R4 is methyl or ethyl and R5 is C1-C5 alkyl; and ii) compounds of the formula I wherein R1 and R2, each independently of the other, is methoxy or ethoxy, R3 is methyl or cyclopropyl, R4 is methyl and R5 is methyl or ethyl.
The formula I also includes compounds wherein R1 and R2, each independently of the other, is methoxy, ethoxy or dimethylamino, R3 is cyclopropylmethyl or, when at least one of R1 and R2 is dimethylamino, C,--C, alkyl or C3-C6 cycloalkyl, R4 is methyl or ethyl, and R5 is C1C5 alkyl.
The compounds of the formula I may be obtained by methods of known type, for example by reacting a compound of the formula II
in which R1 and R2 are as defined in formula I and X is a halogen atom, in particular a chlorine or bromine atom, in the presence of a base with a compound of the formula III
in which R4 and R5 are as defined in formula I.
The process is suitably carried out at a reaction temperature between 200 and +80"C, usually between -10" and +40"C, at normal or elevated pressure and preferably in a solvent or diluent which is inert to the reactants. Suitable solvents or diluents for the reaction are for example: ethers and ethereal compounds, such as dipropyl ether, dioxan, dimethoxyethane and tetrahydrofuran; amides, such as N,N-dialkylated carboxamides; aliphatic, aromatic and halogenated hydrocarbons, in particular benzene, toluene, xylenes, methylene chloride, chloroform and chlorobenzene; nitriles, such as acetonitrile; dimethyl sulphoxide; and ketones, such as acetone and methyl ethyl ketone.
Suitable bases for the above reaction are tertiary amines, such as triethylamine, dimethyl aniline, pyridine, picolines and lutidines, and hydroxides, oxides, carbonates and bicarbonates of alkali metals and alkaline earth metals as well as alkali metal alcoholates, for example potassium tert.butylate and sodium methylate.
The starting materials of the formula III are known (cf. R. WEGLER: "Chemie der Pflanzenschutz- und Schädlingsbekämpfungsmittel", Springer Verlag 1970, pp. 219-245) or they can be prepared in accordance with known methods.
The starting materials of the formula II are new. They can also be prepared by known methods, for example when X is Cl by reacting a compound of the formula lv
wherein R1, R2 and R3 are as defined in formula I, in the presence of a base, with sulphur dichloride (SCI2).
According to the present invention, there is provided a method of combating insects at a locus which method comprises applying to the locus a compound of the formula 1.
The compounds of the formula I are suitable in particular for combating insects which are harmful to plants and animals, for example insects of the families: Acrididae, Blattidae, Gryllidae, Gryllotalpidae, Tettigoniidae, Cimicidae, Pyrrhocoridae, Reduviidae, Aphididae, Delphacidae, Pseudococcidae, Chrysomelidae, Coccinellidae, Bruchidae, Scarabaeidae, Dermestididae, Tenebrionidae, Curculionidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Galleridae, Culicidae, Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Trypetidae and Pucilidae. The locus of application therefore suitably comprises agricultural or horticultural crops or plants.
The compounds of the formula I can thus be used according to the invention for combating insects which damage plants in crops of cotton, vegetable and fruit.
In this connection, particular mention is to be made of the fact that individual compounds of the formula I have both a systemic and a stomach poison and contact action against sucking insects, for example aphids.
The action of the compounds of the formula I can be substantially broadened and adapted to prevailing circumstances by the addition of other insecticides and/or acaridies. Examples of suitable additives are: other organic phosphorus compounds, nitrophenols and derivatives thereof, formamidines, ureas, pyrethroids, carbamates, and chlorinated hydrocarbons.
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 diluents or carries and liquid diluents with surface active agents 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.
For application, the compounds of the formula I may be processed to dusts, emulsifiable concentrates, granules, dispersions, sprays, solutions, or suspensions, in the conventional formulations which is commonly employed in application technology.
The compositions of the present invention may be 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: Dusting, 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 higher concentrations 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 manufacture a) a 5% and b) a 2% dust: a) 5 parts of active substance, 95 partsoftalc; b) 2 parts of active substance, part of highly disperse silicic acid, 97 parts of talc.
The active substances are mixed with the carriers and ground.
Granules The following substances are used to produce 5% 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 dissolved with 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 powder: 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 lignin sulphonate, part of sodium dibutylnaphthalenesulphonate, 54 parts of silicic acid.
b) 25 parts of active substance, 4.5 parts of calcium lignin sulphonate 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 1.5 parts of sodium dibutylnapthalenesulphonate, 19.5 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-polyoxyethyleneethanol, 1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 8.3 parts of sodium aluminium silicate, 16.5 parts of kieselguhr, 46 parts of kaolih; 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 combination emulsifier consisting of fatty alcohol polyglycol ether and alkylarylsulphonate 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 cyclohexanone, 20 parts of xylene.
By diluting these concentrates with water it is possible to obtain emulsions of the required concentration.
Spray: The following ingredients are used to prepare a) a 5% 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 ), 7-dimethyl-5-oxa-4, 7, 9-triaza-2 ,8-dithia-6-oxo-9-dimethylphosphoryl- decane(3) To a solution of 15.3 g of S-methyl-N-(methyl-carbamoyl)-oxythioacetamidate in 100 ml of methylene chloride were added dropwise at a temperature of 0 C 19.5 g of dimethylphosphoryl-N-methylamide-sulphenyl chloride and subsequently 12 g of pyridine. The reaction mixture was stirred for a further 12 hours at 0 to 50C. The reaction solution was filtered by suction and the methylene chloride distilled off. The crude product was dissolved in benzene, and the benzene solution was filtered by suction and the benzene off. The product was chromatographed (silica gel 60/methyl acetate), affording the compound of the formula
(compound 1) with a melting point of 520-560C.
The following compounds of the formula I
are obtained, or can be obtained, in analogous manner:
Compound Rl R2 R3 R4 Rs Physical data 2 CH30 CH30 CH3 CH3 C2H5 n2D0: 1.5190 ----------- CH3 C2Hs nD: 1.5190 10 3 C2H5O C2HsO CH3 CH CH3 1.5133 20 4 C2HsO C2HsO CH3 CH3 C2Hs nD:l.5171 5 C2Hs 0 C2HsO C,H, O CH3 CH3 n2D0: 1.5168 6 (CH3)2N- | (CH3)2N- CH CH3 CH3 7 CH,0 C3 C2Hs CH3 n2D0 CH3O CH3O CH3 C,H, CH, 20 8 CH3O CH3O C2Hs CH3 CH3 n2D0: 1.5186 9 CH3O CHaO (n)C4H9 CH3 CH3 10 CHO CH3O (n)C4H9 CH3 C2H5 n2D0: 1.5142 11 CH30 CH3 D CH2 CH3 CH, 20 11 CH3O CH3O nD: 1.5137 CH3 CH3 13 C,H,O C,H, O CH, CH, (n)C,H,, 14 CH,O CH,O (n)C,H,, CH, CH, 15 CH3O (CH3)2N- CH3 CH3 CH3 Example 2.
Insecticidal action: Spodoptera littoralis, Dl?sdercus fasciatus and Heliothis virescens Cotton plants were sprayed with an aqueous emulsion containing 0.05% of the compound to be tested (obtained from a 10% emulsifiable concentrate).
After the spray coating had dried, the plants were populated with Spodoptera littoralis or Heliothis virescens larvae in the L3 stage or with Dysdercus fasciatus nymphs. Two plants were used for each test compound and insect species.
Evaluation of mortality was made after 2, 4, 8 24 and 48 hours. The test was carried out at 240C and 60, relative humidity. In this test, the compounds of Example I exhibited a positive action against larvae of the species Spodoptera littoralis, Heliothis virescens, and nymphs of the species Dysdercus fasciatus.
Example 3.
Insecticidal action.. Pseudococcus citri Plants (Vicia faba) which have been reared in pots and cut back to a welldeveloped leaf-pair, were populated with approx. 200 lice of the species Pseudococcus citri 24 hours before the start of the test. The undersides of the leaves populated with lice were then sprayed dripping wet next day with a test solution containing 500 ppm of the compound to be tested. Two plants were used for each test and evaluation of mortality was made 4, 24 and 48 hours after the start of the test.
In the above test, the compounds of Example l exhibited a positive action against insects of the species Pseudococcus citri.
Example 4.
Systemic action against Aphis fabae Bean plants which had well developed, roots were transplanted into pots containing 600 ccm of soil and then 50 ml of a solution containing 50 ppm, 10 ppm or l ppm of the compound to be tested (obtained from 25% wettable powder) were poured directly onto the soil.
After 24 hours the parts of the plants above the soil were populated with aphids of the species Aphis fabae and a plastic cylinder was then slipped over the plants to protect the aphids from any possible contact with the test substance either directly or via the gas phase.
The evaluation of mortality was made 48 and 72 hours respectively after the start of the test. Two plants, each in a separate pot, were used per concentration of test substance. The test was carried out at 250C and 70% relative humidity.
In this test, compounds of Example 1 exhibited a positive systemic action against Aphis fabae.
WHAT WE CLAIM IS: 1. A compound of the formula I
wherein R1 and R2, each independently of the other, is methoxy, ethoxy or dimethylamino, R3 is C1-C6 alkyl, C3Ce cycloalkyl or cyclopropylmethyl, R4 is methyl or ethyl and R5 is C1-C5 alkyl.
2. A compound as claimed in claim l wherein R1 and R2, each independently of the other, is methoxy or ethoxy.
3. A compound as claimed in claim I or claim 2 wherein R4 is methyl.
4. A compound as claimed in any of claims l to 3 wherein R5 is methyl or ethyl.
5. A compound as claimed in any one of claims 1 to 4 wherein Era is C1-C4 alkyl, cyclopropyl, cyclohexyl or cyclopropylmethyl.
6. A compound as claimed in claim 5 wherein R3 is methyl, ethyl or cyclopropyl.
7. A compound of the formula I of claim 1 wherein R1 and R2, each independently of the other, is methoxy, ethoxy or dimethylamino, R3 is methyl or ethyl, R4 is methyl or ethyl, and R5 is C1-C5 alkyl.
8. A compound of the formula I of claim l wherein R1 and R2, each independently of the other, is methoxy, ethoxy or dimethylamino, Ra is cyclopropylmethyl or, when at least one of R, and R2 is dimethylamino, C1-C8 alkyl or C3C8 cycloalkyl, R4 is methyl or ethyl, and R, is C1Cs alkyl.
9. The compound of the formula
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (32)

**WARNING** start of CLMS field may overlap end of DESC **. Example 3. Insecticidal action.. Pseudococcus citri Plants (Vicia faba) which have been reared in pots and cut back to a welldeveloped leaf-pair, were populated with approx. 200 lice of the species Pseudococcus citri 24 hours before the start of the test. The undersides of the leaves populated with lice were then sprayed dripping wet next day with a test solution containing 500 ppm of the compound to be tested. Two plants were used for each test and evaluation of mortality was made 4, 24 and 48 hours after the start of the test. In the above test, the compounds of Example l exhibited a positive action against insects of the species Pseudococcus citri. Example 4. Systemic action against Aphis fabae Bean plants which had well developed, roots were transplanted into pots containing 600 ccm of soil and then 50 ml of a solution containing 50 ppm, 10 ppm or l ppm of the compound to be tested (obtained from 25% wettable powder) were poured directly onto the soil. After 24 hours the parts of the plants above the soil were populated with aphids of the species Aphis fabae and a plastic cylinder was then slipped over the plants to protect the aphids from any possible contact with the test substance either directly or via the gas phase. The evaluation of mortality was made 48 and 72 hours respectively after the start of the test. Two plants, each in a separate pot, were used per concentration of test substance. The test was carried out at 250C and 70% relative humidity. In this test, compounds of Example 1 exhibited a positive systemic action against Aphis fabae. WHAT WE CLAIM IS:
1. A compound of the formula I
wherein R1 and R2, each independently of the other, is methoxy, ethoxy or dimethylamino, R3 is C1-C6 alkyl, C3Ce cycloalkyl or cyclopropylmethyl, R4 is methyl or ethyl and R5 is C1-C5 alkyl.
2. A compound as claimed in claim l wherein R1 and R2, each independently of the other, is methoxy or ethoxy.
3. A compound as claimed in claim I or claim 2 wherein R4 is methyl.
4. A compound as claimed in any of claims l to 3 wherein R5 is methyl or ethyl.
5. A compound as claimed in any one of claims 1 to 4 wherein Era is C1-C4 alkyl, cyclopropyl, cyclohexyl or cyclopropylmethyl.
6. A compound as claimed in claim 5 wherein R3 is methyl, ethyl or cyclopropyl.
7. A compound of the formula I of claim 1 wherein R1 and R2, each independently of the other, is methoxy, ethoxy or dimethylamino, R3 is methyl or ethyl, R4 is methyl or ethyl, and R5 is C1-C5 alkyl.
8. A compound of the formula I of claim l wherein R1 and R2, each independently of the other, is methoxy, ethoxy or dimethylamino, Ra is cyclopropylmethyl or, when at least one of R, and R2 is dimethylamino, C1-C8 alkyl or C3C8 cycloalkyl, R4 is methyl or ethyl, and R, is C1Cs alkyl.
9. The compound of the formula
10. The compound of the formula
l l. The compound of the formula
12. The compound of the formula
13. The compound of the formula
14. Compound numbered hereinbefore identified in Example 1.
15. Compounds numbered 8 to 11 and 13 to 15 hereinbefore identified in Example 1.
16. Compounds numbered 7 and 12 hereinbefore identified in Example 1.
17. An insecticidal composition comprising a compound as claimed in any one of claims l to 6, 8, 13 and 15 either together with a solid diluent or carrier therefor or together with a liquid diluent therefor and a surface active agent.
18. An insecticidal composition as claimed in claim 17 in the form of a wettable powder, emulsifiable concentrate, granulate or dispersion.
19. An insecticidal composition comprising a compound as claimed in any one of claims 7, 9 to 12 and 14 either together with a solid diluent or carrier therefor or together with a liquid diluent therefor and a surface active agent.
20. An insecticidal composition as claimed in claim 19 in the form of a wettable powder, emulsifiable concentrate, granulate or dispersion.
21. An insecticidal composition comprising a compound as claimed in claim 16 either with a solid diluent or carrier therefor or together with a liquid diluent therefor and a surface active agent.
22. An insecticidal composition as claimed in claim 21 in the form of a wettable powder, emulsifiable concentrate, granulate or dispersion.
23. A method of combating insects at a locus, which method comprises applying to said locus a compound as claimed in any one of claims 1 to 6, 8, 13 and 15.
24. A method as claimed in claim 23 wherein the locus comprises agricultural or horticultural crops or plants.
25. A method of combating insects at a locus, which method comprises applying to said locus a compound as claimed in any one of claims 7,9 to 12 and 14.
26. A method as claimed in claim 25 wherein the locus comprises agricultural or horticultural crops or plants.
27. A method of combating insects at a locus, which method comprises applying to said locus a compound as claimed in claim 16.
28. A method as claimed in claim 27 wherein the locus comprises agricultural or horticultural crops or plants.
29. A process for the production of a compound of the formula I
wherein R1, R2, Ra, R4 and R5 have the meanings given in claim 1, which process comprises reacting a corresponding compound of the formula II
wherein X represents a halogen atom, with a compound of the formula III
wherein R4 and R5 have the meanings given in claim l, said reaction being conducted in the presence of a base.
30. A process as claimed in claim 29 wherein, in the compound of the formula II and in the compound of the formula I Ra represents a methyl or ethyl group.
31. A process for the production of a compound of the formula I as defined in claim l, substantially as hereinbefore described in Example l.
32. A compound as claimed in claim I produced by the process claimed in any one of claims 29 to 31.
GB47923/77A 1976-11-18 1977-11-17 Phosphorus-containing thiosubstituted carbamic acid derivatives Expired GB1591282A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH1452576A CH627621A5 (en) 1976-11-18 1976-11-18 Pesticide containing thio-substituted carbamic acid derivatives
CH678877A CH633681A5 (en) 1977-06-02 1977-06-02 Pesticide containing thio-substituted carbamic acid derivatives
CH1238977 1977-10-11

Publications (1)

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GB1591282A true GB1591282A (en) 1981-06-17

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JP (1) JPS5365826A (en)
BR (1) BR7707652A (en)
CA (1) CA1175441A (en)
DE (1) DE2751028C2 (en)
EG (1) EG12906A (en)
FR (1) FR2371457A1 (en)
GB (1) GB1591282A (en)
IL (1) IL53409A (en)
IT (1) IT1087238B (en)
MX (1) MX4900E (en)
NL (1) NL7712459A (en)
TR (1) TR19910A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4081536A (en) * 1977-02-04 1978-03-28 The Upjohn Company N-[(phosphinyl) amino]thio- and N-[(phosphinothioyl)amino]-thio-methylcarbamates and methods for controlling insects

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EG12906A (en) 1980-10-31
MX4900E (en) 1982-12-14
BR7707652A (en) 1978-06-13
NL7712459A (en) 1978-05-22
TR19910A (en) 1980-04-28
CA1175441A (en) 1984-10-02
FR2371457B1 (en) 1980-06-13
IT1087238B (en) 1985-06-04
IL53409A0 (en) 1978-01-31
JPS5365826A (en) 1978-06-12
FR2371457A1 (en) 1978-06-16
IL53409A (en) 1981-10-30
DE2751028C2 (en) 1986-08-28
DE2751028A1 (en) 1978-06-01

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Legal Events

Date Code Title Description
PS Patent sealed [section 19, patents act 1949]
48S Specification amended (sect. 8/1949)
SPA Amended specification published
PCNP Patent ceased through non-payment of renewal fee