Title:
INSECTICIDAL AND ACARICIDAL SUBSTITUTED CARBANILIC ACID ESTERS
Document Type and Number:
United States Patent 3800037
Abstract:
Substituted carbanilic acid propargyl esters of the formula ##SPC1## In which R1, R2 and R4, which may be the same or different, each represents a hydrogen atom or a halogen atom or an alkyl, alkoxy or halogenalkyl radical each having from one to four carbon atoms or a --NO2 or --SCN group, and R4 and R5, which may be the same or different, each represents a hydrogen atom or an alkyl group having from one to four carbon atoms, used as synergistic agents for insecticidally and/or a acaricidally active substances.
Inventors:
Martin, Henry (Basel, CH)
Pissiotas, Georg (Loerrach, DT)
Rohr, Otto (Therwil, CH)
Pissiotas, Georg (Loerrach, DT)
Rohr, Otto (Therwil, CH)
Plaque It!
Sponsored by: Flash of Genius |
Application Number:
05/069887
Publication Date:
03/26/1974
Filing Date:
09/04/1970
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Export Citation:
Assignee:
Ciba-Geigy Corporation (Midland, MI)
Primary Class:
Other Classes:
514/530, 514/120, 514/467, 514/123, 514/531, 514/407, 514/79
International Classes:
A01N37/22; A01N47/20; C07C271/06; A01N47/10; C07C271/00; A01N9/08
Field of Search:
424/300,314,186
US Patent References:
Other References:
The Merck Index, 8th Ed., Merch & Co., Inc. 1968, pp. 30-31. .
The Merck Index, 8th Ed., Merch & Co., Inc. 1968, p. 149. .
The Merck Index, 8th Ed., Merch & Co., Inc. 1968, p. 639..
Primary Examiner:
Meyers, Albert T.
Assistant Examiner:
Robinson, Douglas W.
Claims:
We claim
1. An insecticidal and acaricidal composition consisting essentially of equal parts by weight of (1) 2-(1',3'-dioxalan-2'-yl)-phenyl-N-methyl carbamate and (2) a synergist compound selected from the group consisting of N-(2-nitrophenyl)-propargyl carbamate, N-(2-bromophenyl)-propargyl carbamate, N-(3-bromophenyl)propargyl carbamate, N-(2-chlorophenyl propargyl carbamate, N-(4-chlorophenyl)-propargyl carbamate, N-(2,3-dichlorophenyl)-propargyl carbamate, N-(2,5-dichlorophenyl)propargyl carbamate, N-(3,5-dichlorophenyl)-propargyl carbamate, N-(2,4,5-trichlorophenyl)-propargyl carbamate, N-(3-trifluoromethylphenyl)-propargyl carbamate, N-(3-methylphenyl)-propargyl carbamate, N-(4-fluorophenyl)-propargyl carbamate, N-(2-methyl-3-chlorophenyl)-propargyl carbamate, N-(2,5-dimethylphenyl)-propargyl carbamate and N-(2-chloro-5-trifluoromethylphenyl)-propargyl carbamate.
2. The composition of claim 1 in which the synergist compound is N-(2-nitrophenyl)-propargyl carbamate.
3. The composition of claim 1 in which the synergist compound is N-(2-bromophenyl)-propargyl carbamate.
4. The composition of claim 1 in which the synergist compound is N-(3-bromophenyl)-propargyl carbamate.
5. The composition of claim 1 in which the synergist compound is N-(2-chlorophenyl)-propargyl carbamate.
6. The composition of claim 1 in which the synergist compound is N-(4-chlorophenyl)-propargyl carbamate.
7. The composition of claim 1 in which the synergist compound is N-(2,3-dichlorophenyl)-propargyl carbamate.
8. The composition of claim 1 in which the synergist compound is N-(2,5-dichlorophenyl)-propargyl carbamate.
9. The composition of claim 1 in which the synergist compound is N-(3,5-dichlorophenyl)-propargyl carbamate.
10. The composition of claim 1 in which the synergist compound is N-(2,4,5-trichlorophenyl)-propargyl carbamate.
11. The composition of claim 1 in which the synergist compound is N-(3-trifluoromethylphenyl)-propargyl carbamate.
12. The composition of claim 1 in which the synergist compound is N-(3-methylphenyl)-propargyl carbamate.
13. The composition of claim 1 in which the synergist compound is N-(4-fluorophenyl)-propargyl carbamate.
14. The composition of claim 1 in which the synergist compound is N-(2-methyl-3-chlorophenyl)-propargyl carbamate.
15. The composition of claim 1 in which the synergist compound is N-(2,5-dimethylphenyl)-propargyl carbamate.
16. The composition of claim 1 in which the synergist compound is N-(2-chloro-5-trifluoromethylphenyl)-propargyl carbamate.
17. An insecticidal and acaricidal composition consisting essentially of equal parts by weight of (1) a pesticidal compound selected from the group consisting of 1-naphthyl-Nmethyl carbamate, 2-isopropoxyphenyl-N-methyl carbamate, 1-Isopropyl-3-methylpyrazol-5-yl-N,N-dimethyl carbamate, 2-[Propargylmethylamino]-phenyl-N-methylcarbamate, O,O-Dimethyl-S- (1,2-dicarbethoxyethyl) dithiophosphate, 2-Chloro-2-diethylcarbamoyl-1-methlvinyldimethylphosphate, O,O-Dimethyl-S-[ 2-methoxy-1,3,4-thiadiazol-5-(4H)-onyl-4-methyl]dithiopho sphate and pyrethrum and (2) N-(2-nitrophenyl)-propargyl carbamate.
18. The composition of claim 17 in which the pesticidal compound is 1-naphthyl-N-methyl carbamate.
19. The composition of claim 17 in which the pesticidal compound is 2-isopropoxyphenyl-N-methyl carbamate.
20. The composition of claim 17 in which the pesticidal compound is 1-Isopropyl-3-methylpyrazol-5-yl-N,N-dimethylcarbamate.
21. The composition of claim 17 in which the pesticidal compound is 2-[propargylmethylamino]-phenyl-N-methylcarbamate.
22. The composition of claim 17 in which the pesticidal compound is O,O-Dimethyl-S-(1,2-dicarbethoxyethyl) dithiophosphate.
23. The composition of claim 17 in which the pesticidal compound is 2-Chloro-2-diethylcarbamoyl-1-methylvinyldimethylphosphate.
24. The composition of claim 17 in which the pesticidal compound is O,O Dimethyl-S-[2-methoxy-1,3,4--thiadiazol-5-(4H)-onyl-(4)-methyl] dithiophosphate.
25. The composition of claim 17 in which the pesticidal compound is pyrethrum.
26. A method of combatting insects and representatives of the order acarina, which comprises applying thereto an insecticidally and acaricidally effective amount of the composition of claim 1.
27. A method of combatting insects and representatives of the order acarina, which comprises applying thereto an insecticidally and acaricidally effective amount of the composition of claim 17.
1. An insecticidal and acaricidal composition consisting essentially of equal parts by weight of (1) 2-(1',3'-dioxalan-2'-yl)-phenyl-N-methyl carbamate and (2) a synergist compound selected from the group consisting of N-(2-nitrophenyl)-propargyl carbamate, N-(2-bromophenyl)-propargyl carbamate, N-(3-bromophenyl)propargyl carbamate, N-(2-chlorophenyl propargyl carbamate, N-(4-chlorophenyl)-propargyl carbamate, N-(2,3-dichlorophenyl)-propargyl carbamate, N-(2,5-dichlorophenyl)propargyl carbamate, N-(3,5-dichlorophenyl)-propargyl carbamate, N-(2,4,5-trichlorophenyl)-propargyl carbamate, N-(3-trifluoromethylphenyl)-propargyl carbamate, N-(3-methylphenyl)-propargyl carbamate, N-(4-fluorophenyl)-propargyl carbamate, N-(2-methyl-3-chlorophenyl)-propargyl carbamate, N-(2,5-dimethylphenyl)-propargyl carbamate and N-(2-chloro-5-trifluoromethylphenyl)-propargyl carbamate.
2. The composition of claim 1 in which the synergist compound is N-(2-nitrophenyl)-propargyl carbamate.
3. The composition of claim 1 in which the synergist compound is N-(2-bromophenyl)-propargyl carbamate.
4. The composition of claim 1 in which the synergist compound is N-(3-bromophenyl)-propargyl carbamate.
5. The composition of claim 1 in which the synergist compound is N-(2-chlorophenyl)-propargyl carbamate.
6. The composition of claim 1 in which the synergist compound is N-(4-chlorophenyl)-propargyl carbamate.
7. The composition of claim 1 in which the synergist compound is N-(2,3-dichlorophenyl)-propargyl carbamate.
8. The composition of claim 1 in which the synergist compound is N-(2,5-dichlorophenyl)-propargyl carbamate.
9. The composition of claim 1 in which the synergist compound is N-(3,5-dichlorophenyl)-propargyl carbamate.
10. The composition of claim 1 in which the synergist compound is N-(2,4,5-trichlorophenyl)-propargyl carbamate.
11. The composition of claim 1 in which the synergist compound is N-(3-trifluoromethylphenyl)-propargyl carbamate.
12. The composition of claim 1 in which the synergist compound is N-(3-methylphenyl)-propargyl carbamate.
13. The composition of claim 1 in which the synergist compound is N-(4-fluorophenyl)-propargyl carbamate.
14. The composition of claim 1 in which the synergist compound is N-(2-methyl-3-chlorophenyl)-propargyl carbamate.
15. The composition of claim 1 in which the synergist compound is N-(2,5-dimethylphenyl)-propargyl carbamate.
16. The composition of claim 1 in which the synergist compound is N-(2-chloro-5-trifluoromethylphenyl)-propargyl carbamate.
17. An insecticidal and acaricidal composition consisting essentially of equal parts by weight of (1) a pesticidal compound selected from the group consisting of 1-naphthyl-Nmethyl carbamate, 2-isopropoxyphenyl-N-methyl carbamate, 1-Isopropyl-3-methylpyrazol-5-yl-N,N-dimethyl carbamate, 2-[Propargylmethylamino]-phenyl-N-methylcarbamate, O,O-Dimethyl-S- (1,2-dicarbethoxyethyl) dithiophosphate, 2-Chloro-2-diethylcarbamoyl-1-methlvinyldimethylphosphate, O,O-Dimethyl-S-[ 2-methoxy-1,3,4-thiadiazol-5-(4H)-onyl-4-methyl]dithiopho sphate and pyrethrum and (2) N-(2-nitrophenyl)-propargyl carbamate.
18. The composition of claim 17 in which the pesticidal compound is 1-naphthyl-N-methyl carbamate.
19. The composition of claim 17 in which the pesticidal compound is 2-isopropoxyphenyl-N-methyl carbamate.
20. The composition of claim 17 in which the pesticidal compound is 1-Isopropyl-3-methylpyrazol-5-yl-N,N-dimethylcarbamate.
21. The composition of claim 17 in which the pesticidal compound is 2-[propargylmethylamino]-phenyl-N-methylcarbamate.
22. The composition of claim 17 in which the pesticidal compound is O,O-Dimethyl-S-(1,2-dicarbethoxyethyl) dithiophosphate.
23. The composition of claim 17 in which the pesticidal compound is 2-Chloro-2-diethylcarbamoyl-1-methylvinyldimethylphosphate.
24. The composition of claim 17 in which the pesticidal compound is O,O Dimethyl-S-[2-methoxy-1,3,4--thiadiazol-5-(4H)-onyl-(4)-methyl] dithiophosphate.
25. The composition of claim 17 in which the pesticidal compound is pyrethrum.
26. A method of combatting insects and representatives of the order acarina, which comprises applying thereto an insecticidally and acaricidally effective amount of the composition of claim 1.
27. A method of combatting insects and representatives of the order acarina, which comprises applying thereto an insecticidally and acaricidally effective amount of the composition of claim 17.
Description:
This invention relates to substituted carbanilic acid propargyl esters which may be used as synergistic agents for insecticidally and/or acaricidally active substances, and to preparations which in addition to insecticidal or acaricidal substances contain such carbanilic acid propargyl esters.
The compounds which are used as synergistic agents according to the present invention have the formula ##SPC2##
In which R 1 , R 2 and R 3 , which may be the same or different, each represents a hydrogen atom or a halogen atom or an alkyl, alkoxy or halogenalkyl radical each having from one to four carbon atoms or a --NO 2 or --SCN group, and R 4 and R 5 , which may be the same or different, each represents a hydrogen atom or an alkyl group having from one to four carbon atoms.
The alkyl and alkoxy groups which are represented by R 1 , R 2 , R 3 , R 4 and R 5 , may be substituted or unsubstituted, branched or straight-chained. Suitable alkyl and alkoxy groups are, for example, methyl, ethyl and methoxy groups.
Compounds of special importance are those of the formulae ##SPC3##
In each of which R 6 , R 7 and R 8 , which may be the same or different, each represents a hydrogen, fluorine, chlorine or bromine atom or a methyl, methoxy, --CF 3 . --NO 2 or --SCN group.
An especially suitable compound is that of the formula ##SPC4##
This compound is new and therefore also forms a subject of the invention.
The compounds of the formula I may be prepared according to methods which are, in themselves, known, for example, by the reaction of an isocyanate of the formula ##SPC5##
With an alcohol of the formula ##SPC6##
In an inert solvent, for example, benzene, petroleum ether or dimethylformamide, the substituents R 1 , R 2 , R 3 , R 4 and R 5 having the same meanings as those specified for formula I.
The compounds defined by the general formula I are capable of increasing the activity of insecticidal and/or acaricidal compounds many-fold (synergism). Surprisingly, it has also been found that when using compounds of the formula I, insects or representatives of the order Acarina, which are resistant to carbamates or phosphoric acid esters, can be rendered completely sensitive to these latter compounds. Suitable insecticidally or acaricidally active substances are, for example, the following compounds:
PHOSPHORIC ACID DERIVATIVES
Bis-O,O-diethylphosphoric acid anhydride (TEPP)
O,O,O,O-Tetrapropyldithiopyrophosphate
Dimethyl(2,2,2-trichloro-1-hydroxyethyl)phosphonate (TRICHRORFON)
1,2-Dibromo-1,2-dichlorethyldimethylphosphate (NALED)
2,2-Dichlorovinyldimethylphosphate (DICHLORFOS)
2-Methoxycarbamyl-1-methylvinyldimethylphosphate (MEVINPHOS)
Dimethyl-1-methyl-2-(methylcarbamoyl)vinylphosphate cis (MONOCROTOPHOS)
3-(Dimethoxyphosphinyloxy)-N-methyl-N-methoxy-cis-croton -amide
3-(Dimethoxyphosphinyloxy)-N,N-dimethyl-cis-crotonamide (DICROTOPHOS)
2-Chloro-2-diethylcarbamoyl-1-methylvinyldimethylphospha te (PHOSPHAMIDON)
O,O-Diethyl-O-2-(ethylthio)-ethylthiophosphate (DEMETON)
O,O-Diethyl-S-2-(ethylthio)-ethylthiophosphate
S-Ethylthioethyl-O,O-dimethyl-dithiophosphate (THIOMETON)
O,O-Diethyl-S-ethylmercaptomethyldithiophosphate (PHORATE)
O,O-Diethyl-S-2-[(ethylthio)ethyl]dithiophosphate (DISULFOTON)
O,O-Dimethyl-S-2-(ethylsulphinyl)ethylthiophosphate (OXYDEMETONMETHYL)
O,O-Dimethyl-S-(1,2-dicarbethoxyethyl)dithiophosphate (MALATHION)
(O,O,O,O-Tetraethyl-S,S'-methylene-bis-[dithiophosphate] (ETHION)
O-Ethyl-S,S-dipropyldithiophosphate
O,O-Dimethyl-S-(N-methyl-N-formylcarbamoylmethyl)-dithio phosphate (FORMOTION)
S-N-(1-Cyano-1-methylethyl)carbamoylmethyldiethylthiolph osphate (CYANTHOAT)
S-(2-Acetamidoethyl)-O,O-dimethyldithiophosphate
Hexamethylphosphoric acid triamide (HEMPA)
O,O-Dimethyl-O-p-nitrophenylthiophosphate (PARATHION-METHYL)
O,O-Diethyl-O-p-nitrophenylthiophosphate (PARATHION)
O-Ethyl-O-p-nitrophenylthiophosphonate (EPN)
O,O-Dimethyl-O-(4-nitro-m-tolyl)thiophosphate (FENITROTHION)
O,O-Dimethyl-O-(2-chloro-4-nitrophenyl)thiophosphate (DICAPTHON)
O,O-Dimethyl-O-p-cyanophenylthiophosphate (CYANOX)
O-Ethyl-O-p-cyanophenylphenylthiophosphonate
O,O-Diethyl-O-2,4-dichlorophenylthiophosphate (DICHROFENTHION)
O-2,4-Dichlorophenyl-O-methylisopropylamidothiophosphate
O,O-Dimethyl-O-2,4,5-trichlorophenylthiophosphate (RONNEL)
O-Ethyl-O-2,4,5-trichlorophenylethylthiophosphonate (TRICHLORONAT)
O,O-Dimethyl-O-2,5-dichloro-4-bromophenylthiophosphate (BROMOPHOS)
O,O-Diethyl-O-2,5-dichloro-4-bromophenylthiophosphate (BROMOPHOS-ETHYL)
4-tert. Butyl-2-chlorophenyl-N-methyl-O-methylamidophosphate (CRUFOMAT)
Dimethyl-p-(methylthio)phenylphosphate
O,O-Dimethyl-O-(3-methyl-4-methylmercaptophenyl)thiophos phate (FENTHION)
Isopropylamino-O-ethyl-O-(4-Methylmercapto-3-methylpheny l)phosphate
O,O-Diethyl-O-p-[(methylsulphinyl)phenyl]-thiophosphate (FENSULFOTHION)
O,O-Dimethyl-O-p-sulphamidophenylthiophosphate
O-[p-(Dimethylsulphamido)phenyl]O,O-dimethylthiophosphat e (FAMPHUR)
O,O,O',O' -Tetramethyl-O,O'-thiodi-p-phenylenethiophosphate
O-(p-(p-Chlorophenylazophenyl)O,O-dimethylthiophosphate (AZOTHOAT)
O-Ethyl-S-phenyl-ethyldithiophosphonate
O-Ethyl-S-4-chlorophenyl-ethyldithiophosphonate
O-Isobutyl-S-p-chlorophenyl-ethyldithiophosphonate
O,O-Dimethyl-S-p-chlorophenylthiophosphate
O,O-Dimethyl-S-(p-chlorophenylthiomethyl)-dithiophosphat e
O,O-Diethyl-p-chlorophenylmercaptomethyl-dithiophosphate (CARBONPHENOTHION)
O,O-Diethyl-S-p-chlorophenylthiomethyl-thiophosphate
O,O-Dimethyl-S-(carbethoxy-phenylmethyl)dithiophosphate (PHENOTHOAT)
O,O-Diethyl-S-(carbofluorethoxy-phenylmethyl)-dithiophos phate
O,O-Dimethyl-S-(carbisopropoxy-phenylmethyl)-dithiophosp hate
O,O-Dimethyl-O-(alpha-methylbenzyl-3-hydroxycrotonyl)pho sphate,
2-Chloro-1-(2,4-dichlorophenyl)vinyl-diethylphosphate (CHLORFENVINPHOS)
2-Chloro-1-(2,4,5-trichlorophenyl)vinyl-dimethylphosphat e
O-(2-Chloro-1-(2,5-dichlorophenyl)vinyl)-O,O-diethylthio phosphate
Phenylglyoxylonitriloxime-O,O-diethylthiophosphate (PHOXIM)
O,O-Diethyl-O-(3-chloro-4-methyl-2-oxo-2-H-1-benzopyran- 7-yl)-thiophosphate (COUMAPHOS)
O,O-Diethyl-7-hydroxy-3,4-tetramethylene-coumarinyl-thio phosphate (COUMITHOAT)
2,3-p-Dioxanedithiol-S,S-bis(O,O-diethyldithiophosphate) (DIOXATHION)
2-Methoxy-4-H-1,3,2-benzodioxaphosphorine-2-sulphide
O,O-Diethyl-O-(5-phenyl-3-isooxyzolyl (sic)) thiophosphate
S-[(6-Chlor-2-oxo-3-benzoxazolinyl)methyl]O,O-diethyldit hiophosphate (PHOSALON)
2-(Diethoxyphosphinylimino)-4-methyl-2,3-dithiolane
O,O-Dimethyl-S-[2-methoxy-1,3,4-thiadiazol-5-(4H)-onyl-( 4)-methyl]dithiopho sphate
Tris-(2-methyl-1-aziridinyl)-phosphine-oxide (METEPA)
O,O-Dimethyl-S-phthalimidomethyl-dithiophosphate
S-(2 -Chloro-1-phthalimidoethyl)-O,O-diethyldithiophosphate
N-Hydroxynaphthalimido-diethylphosphate
Dimethyl-3,5,6-trichloro-2-pyridylphosphate
O,O-Dimethyl-O-(3,5,6-trichloro-2-pyridyl)thiophosphate
O,O-Diethyl-O-(3,5,6-trichloro-2-pyridyl)thiophosphate
O,O-Diethyl-O-2-pyrazinylthiophosphate (THIONAZIN) O,O-Diethyl-O-(2-quinoxylyl)thiophosphate
O,O-Dimethyl-S-(4-oxo-1,2,3-benzotriazin-3(4H)-ylmethyl) dithiophosphate (AZINPHOSMETHYL)
O,O-Diethyl-S-(4-oxo-1,2,3-benzotriazin-3(4H)-ylmethyl)d ithiophosphate (AZINPHOSETHYL)
S-[(4,6-Diamino-s-triazin-2-yl)methyl]-O,O-dimethyldithi ophosphate (MENAZON)
S-[2-(Ethylsulphonyl)ethyl]dimethylthiophosphate (DIOXYDEMETON-S-METHYL)
Diethyl-S-[2-(ethylsulphinyl)ethyl]dithiophosphate (OXYDISULFOTON)
Bis-O,O-diethylthiophosphoric acid anhydride (SULFOTEP)
Dimethyl-1,3-di(carbomethoxy)-1-propen-2-yl-phosphate
Dimethyl-(2,2,2-trichloro-1-butyroyloxyethyl)phosphonate (BUTONAT)
O,O-Dimethyl-O-(2,2-dichloro-1-methoxy-vinyl)phosphate
O,o-dimethyl-O-(3-chloro-4-nitrophenyl)thiophosphate (CHLORTHION)
O,O-Dimethyl-O(or S)-2-(ethylthioethyl)thiophosphate (DEMETONS-METHYL)
Bis-(dimethylamido)fluorophosphate (DIMEFOX)
2-(O,O-Dimethyl-phosphoryl-thiomethyl)-5-methoxy-pyrone- 4
3,4-Dichlorobenzyl-triphenylphosphonium chloride
Dimethyl-N-methoxymethylcarbamoylmethyl-dithiophosphate (FORMOCARBAM)
O,O-Diethyl-O-(2,2-dichloro-1-chlorethoxyvinyl)phosphate
O,O-Dimethyl-O-(2,2-dichloro-1-chlorethoxyvinyl)phosphat e
O-Ethyl-S,S-diphenyldithiolphosphate
O-Ethyl-S-benzyl-phenyldithiophosphonate
O,O-Diethyl-S-benzyl-thiophosphate
O,O-Dimethyl-S-(4-chlorophenylthiomethyl)dithiophosphate (METHYLCARBOPHENOTHION)
O,O-Dimethyl-S-(ethylthiomethyl)dithiophosphate
Diisopropylaminofluorophosphate (MIPAFOX)
O,O-Dimethyl-S-(morpholinylcarbamoylmethyl)dithiophospha te (MORPHOTHION)
Bismethylamido-phenylphosphate
O,O-Dimethyl-S-(benzenesulphonyl)dithiophosphate
O,O-Dimethyl-(S and O)-ethylsulphinylethylthiophosphate
O,O-Diethyl-O-4-nitrophenylphosphate
O,O-Diethyl-S-( 2,5-dichlorophenylthiomethyl)dithiophosphate (PHENDAPTON)
Triethoxy-isopropoxy-bis (thiophosphinyl)disulphide
O,O-Diethyl -O-(4-methyl-coumarinyl-7)-thiophosphate (POTASAN)
2-Methoxy-4H-1,3,2-benzodioxaphosphorine-2-oxide
Octamethylpyrophosphoramide (SCHRADAN)
Bis(dimethoxythiophosphinylsulphido)-phenylmethane
5-Amino-bis(dimethylamido)phosphinyl-3-phenyl-1,2,4-tria zole (TRIAMIPHOS)
N-Methyl-5-(O,O-dimethylthiolphosphoryl)-3-thiavaleramid e (VAMIDOTHION) and
N,N,N' ,N'-Tetramethyldiamidofluorophosphate (DIMEFOX)
CARBAMIC ACID DERIVATIVES
1-Naphthyl-N-methylcarbamate (CARBARYL)
2-Butinyl-4-chlorophenylcarbamate
4-Dimethylamino-3,5-xylyl-N-methylcarbamate
4-Dimethylamino-3-tolyl-N-methylcarbamate (AMINOCARB)
3,4,5-Trimethylphenyl-N-methylcarbamate
2-Chlorophenyl-N-methylcarbamate (CPMC)
5-Chlor-6-oxo-2-norbornane-carbonitrile-O-(methylcarbamo yl)-oxime
1-(Dimethylcarbamoyl)-5-methyl-3-pyrazolyl-N,N-dimethylc arbamate (DIMETILAN)
2,3-Dihydro-2,2-dimethyl-7-benzofuranyl-N-methylcarbamat e (CARBOFURAN)
2-Methyl-2-methylthio-propionaldehyde-O-(methylcarbamoyl )oxime (ALDICARB)
8-Quinaldyl-N-methylcarbamate and its salts
Methyl 2-isopropyl-4-(methylcarbamoyloxy)carbanilate
m-(1-Ethylpropyl)phenyl-N-methylcarbamate
3,5-Di-tert.butyl-N-methylcarbamate
m-(1-Methylbutyl)phenyl-N-methylcarbamate
2-Isopropylphenyl-N-methylcarbamate
2-sec.Butylphenyl-N-methylcarbamate
m-Tolyl-N-methylcarbamate
2,3-Xylyl-N-methylcarbamate
3-Isopropylphenyl-N-methylcarbamate
3-tert.Butylphenyl-N-methylcarbamate
3-sec.-Butylphenyl-N-methylcarbamate
3-Isopropyl-5-methylphenyl-N-methylcarbamate (PROMECARB)
3,5-Diisopropylphenyl-N-methylcarbamate
2-Chlor-5-isopropylphenyl-N-methylcarbamate
2-Chloro-4,5-dimethylphenyl-N-methylcarbamate
2-(1,3-Dioxolan-2-yl)phenyl-N-methylcarbamate (DIOXYCARB)
2-(4,5-Dimethyl-1,3-dioxolan-2-yl)phenyl-N-methylcarbama te
2-(1,3-Dioxan-2-yl)phenyl-N-methylcarbamate
2-(1,3-Dithiolan-2-yl)phenyl-N-methylcarbamate
2-(1,3-Dithiolan-2-yl)phenyl-N,N-dimethylcarbamate
2-Isopropoxyphenyl-N-methylcarbamate (ARPROCARB)
2-(2-Propinyloxy)phenyl-N-methylcarbamate
2-(2-Propinyloxy)phenyl-N-methylcarbamate
3-(2-Propinyloxy)phenyl-N-methylcarbamate
2-Dimethylaminophenyl-N-methylcarbamate
2-Diallylaminophenyl-N-methylcarbamate
4-Diallylamino-3,5-xylyl-N-methylcarbamate (ALLYXICARB)
4-Benzothienyl-N-methylcarbamate
2,3-Dihydro-2-methyl-7-benzofuranyl-N-methylcarbamate
3-Methyl-1-phenylpyrazol-5-yl-N,N-dimethylcarbamate
1-Isopropyl-3-methylpyrazol-5-yl-N,N-dimethylcarbamate (ISOLAN)
2-(N',N'-Dimethylcarbamoyl)-3-methylpyrazol-5-yl-N,N-dim ethylcarbamate
2-Dimethylamino-5,6-dimethylpyrimidin-4-yl-N,N-dimethylc arbamate
3-Methyl-4-dimethylaminomethyleneiminophenyl-N-methylcar bamate
3-Dimethylamino-methyleneiminophenyl-N-methylcarbamate
1-Methylthio-ethylimino-N-methylcarbamate (METHOXYMYL)
2-Methylcarbamoyloxyimino-1,3-dithiolane
5-Methyl-2-methylcarbamoyloxyimino- 1,3-oxathiolane
2-(1-Methoxy-2-propoxy)phenyl-N-methylcarbamate
2-(1-Butin-3-yl-oxy)phenyl-N-methylcarbamate
3-Methyl-4 -(dimethylamino-methylmercapto-methyleneimino)phenyl-N-methy lcarbamate
1,3-Bis(carbamoylthio)-2-(N,N-dimethylamino)-propane hydrochloride
5,5-Dimethylhydroresorcinoldimethylcarbamate
2-[Propargylethylamino]-phenyl-N-methylcarbamate
2-[Propargylmethylamino]-phenyl-N-methylcarbamate
2-[Dipropargylamino]-phenyl-N-methylcarbamate
3-Methyl-4-[dipropargylamino]-phenyl-N-methylcarbamate
3,5-Dimethyl-4-[dipropargylamino]-phenyl-N-methylcarbama te
2-[Allyl-isopropylamino]-phenyl-N-methylcarbamate and
3-[Allyl-isopropylamino]-phenyl-N-methylcarbamate.
Chlorinated Hydrocarbons
γ-Hexachlorocyclohexane [Gammerxane; Lindane; γ HCH]
1,2,4,5,6,7,8,8-Octachloro-3α,4,7,7α '-tetrahydro-4,7-methyleneindane [Chlordan]
1,4,5,6,7,8,8-Heptachloro-3α ,4,7,7α -tetrahydro-4,7-methyleneindane [Heptachlor]
1,2,3,4,10,10-Hexachloro-1,4,4α ,5,8,8α-hexahydro-endo-1,4-exo-5,8-dimethanonaphthalene [Aldrin]
1,2,3,4,10,10-Hexachloro-6,7-epoxy-1,4,4α ,5,6,7,8,8α-octahydro-exo-1,4-endo-5,8-dimethanonaphthalene [Dieldrin]
ditto, endo-endo- [Endrin]
6,7,8,9,10,10-Hexachloro-1,5,5α,6,9,9α-hexahydro-6,9-m ethano-2, 3,4 benzo [e]-dioxa-thiepene-3-oxide [Endosulfan]
Chlorinated camphor [Toxaphen] Decachloroctahydro-1,3,4-metheno-2H-cyclobuta[ e d] pentalen-2-one
Dodecachloroctahydro-1,3,4-metheno-1H-cyclobuta[ c d] pentalene [Mirex]
Ethyl-1,1α ,3,3α ,4,5,5,5α ,5α,6-decachloroctahydro-2-hydroxy-1,3,4-metheno-1H-cyclobu ta[ c d] pentalene-2- laevulinate
Bis(pentachloro-2,4-cyclopentadien-1-yl)
Dinoctone
1,1,1-Trichloro-2,2 -bis(p-chlorophenyl)ethane [DDT]
Dichlorodiphenyl-dichloroethane [TDE]
Di(p-chlorophenyl)-trichloromethylcarbinol [Dicofol]
Ethyl-4,4'-dichlorophenylglycollate [Chlorobenzylate]
Ethyl-4,4'-dibromobenzylate [Bromobenzylate]
Isopropyl-4,4'-dichlorobenzylate
1,1,1-Trichloro-2,2 bis(p-methoxyphenyl)ethane [Methoxychlor]
Diethyl-diphenyl-dichloroethane
Decachloropentacyclo( 3,3,2, O 2 ,6, O 3 ,9, O 7 ,10 )decan-4-one [Chlordecon].
NITROPHENOLS AND DERIVATIVES
4,6-Dinitro-6-methylphenol Na salt [dinitrocresol]
Dinitrobutylphenol-2,2',2"-triethanolamine salt
2-Cyclohexyl-4,6-dinitrophenol [Dinex]
2-(1-Methylheptyl)-4,6-dinitrophenyl-crotonate [Dinocap]
2 sec.-Butyl-4,6-dinitrophenyl-3-methyl-butenoate [Binapacryl]
2 sec.-Butyl-4,6-dinitrophenyl-cyclopropionate and
2 sec.-Butyl-4,6-dinitrophenyl-isopropyl-carbonate [Dinobuton]
VARIOUS SUBSTANCES
Sabadilla
Rotenone
Cevadine
Veratridine
Ryania
Pyrethrin
3-Allyl-2-methyl-4-oxo-2-cyclopenten-1-yl-chrysanthemuma te (Allethrin)
6-Chloropiperonyl-chrysanthemumate (Barthrin)
2,4-Dimethylbenzyl-chrysanthemumate (Dimethrin)
2,3,4,5-Tetrahydrophthalimidomethyl-chrysanthemumate
(5-Benzyl-3-furyl)-methyl-2,2-dimethyl-3-(2-methylpropan yl)cyclopropanecarb oxylate
Nicotine
Bacillus thuringiensis Berliner
Dicyclohexylcarbodiimide
Diphenyldiimide [azobenzene (sic)]
4-Chlorobenzyl-4-chlorophenylsulphide [Chlorobenside]
Creosote oil
6-Methyl-2-oxo-1,3-dithiolo-[4,5-b]-quinoxaline [Quinomethionate]
(I)-3-(2-Furfuryl)-2-methyl-4-oxocyclopent-2-enyl(I)-(ci s+trans)chrysanthem um-monocarboxylate [Furethrin]
2-Pivaloyl-indane-1,3-dione [Pindon]
2-Fluorethyl(4-bisphenyl)acetate
2-Fluoro-N-methyl-N(1-naphthyl)-acetamide
Pentachlorophenol and salts
2,2,2-Trichloro-N-(pentachlorophenyl)-acetimidoyl chloride
N'-(4-Chloro-2-methylphenyl)-N,N-dimethylformamidine (Chlorphenamidine)
4-Chlorobenzyl-4-fluorophenyl-sulphide (Fluorobenside)
5,6-Dichloro-1-phenoxycarbanyl-2-trifluoromethyl-benzimi dazole (Fenozaflor)
Tricyclohexyl-stannic-hydroxide
2-Thiocyanatoethyl-lauric acid ester
β-Butoxy-β'-thiocyanatodiethyl-ether
Isobornyl-thiocyanatoacetate
p-Chlorophenyl-p-chlorobenzenesulphonate (Ovex)
2,4-Dichlorophenyl-benzenesulphonate
p-Chlorophenyl-benzenesulphonate (Fenson)
p-Chlorphenyl-2,4,5-trichlorophenylsulphone (Tetradifon)
p-Chlorophenyl-2,4,5-trichlorophenylsulphide (Tetrasul)
Methyl bromide
p-Chlorophenyl-phenylsulphone
p-Chlorobenzyl-p-chlorophenylsulphide (Chlorobenside)
4-Chlorophenyl-2,4,5-trichlorophenylazosulphide
2(p-tert.-Butylphenoxy)-1-methylethyl-2-chloroethyl-sulp hite
2(p-tert.-Butylphenoxy)cyclohexyl-2-propinyl-sulphite
4,4'-Dichloro-N-methylbenzenesulphonanilide
N-(2-Fluoro-1,1,2,2-tetrachloroethylthio)-methanesulphon anilide
2-Thio-1,3-dithiolo-(4,5-6)quinoxaline (Thioquinox)
Chloromethyl-p-chlorophenylsulphone (lauseto (sic!) new)
1,3,6,8-Tetranitrocarbazole and
Prop-2-ynyl-(4-t-butylphenoxy)-cyclohexylsulphite (Propargil).
The ratio of the insecticidally and/or acaricidally active substance to the compounds of the formula I is preferably within the range of from 0.01:10 to 200:1.
Such synergistically active mixtures can preferentially be employed against all harmful insects, for example against aphids, such as the green peach aphid (Myzus persicae), and the black bean aphid (Doralis fabae); scale insects lice such as Aspidiotus hederae, Lecanium hesperidium, Pseudococcus maritimus; Thysanoptera such as Hercinothrios femoralis, and bugs such as the beet bug (Piesma quadrata) or the bed bug (Cimex lectularius), caterpillars, such as Plutella maculipennis and Lymantria dispar; weevils such as the granary weevil (Calandra granaria) or the Colorado beetle (Leptinotarsa decemlineata), but also varieties which live in soil, such as wireworms (Agriotes sp.) or cockchafer grubs (Melolontha melolontha); cockroaches, such as the German cockroach (Blattella germanica); Orthoptera, such as the cricket (Gryllus domesticus); termites, such as Beticulitermes; Hymenoptera, such as ants; Diptera, such as the vinegar fly (Drosophila melanogaster), the Mediterranean fruit fly (Ceratitis capitata), the housefly (Musca domestica), and gnats, such as the yellow fever mosquito (Aedes aegypti).
The use of this synergistic mixture is also especially effective in combatting representatives of the order Acarina such as for example Eulaelaps, Echinolaelaps, Laelaps, Haemogamasus, Dermanyssus, Ornithonyssus, Allodermanyssus, in particular Allodermanyssus sanguineus, Pneumonyssus, Amblyomma, Aponomma, Boophilus, Dermacentor, Haemophysalis, Hyalomma, Ixodes, Margaropus, Rhipicephalus, Ornithodorus; Octobius, Cheyletidae, for example Cheyletus, Psorergates, Demodicidae, Trombiculidae, for example Trombicula, Eutrombicula, Schongastia, Acomatacurus, Neoschongastia, Euschongastia, Sarcoptiformes for example Notoedres, Sarcoptes, Knemidokoptes, Psoroptidae, for example Psoroptes, Chorioptes, otodectes or Tetranychidae, for example Tetranychus telarius; Tetranychus urticae and the like.
The mixtures can either be used by themselves or together with suitable carriers and/or additives.
Suitable carriers and additives can be solid or liquid and correspond to the substances which are customary in formulation technology, for example, natural or regenerated mineral substances, solvents, dispersing agents, wetting agents, adhesives, thickeners, binders or fertilisers.
Such preparations can be employed in the form of solutions, emulsions, suspensions, granules or dusting agents. The methods of application depend on the end uses and must ensure that the active substance can be finely distributed.
The content of active substance in the preparations described above is between 0.1 and 95 percent. At the same time it should be mentioned that in the case of application from aircraft or by means of other suitable application instruments, concentrations of up to 99.5 percent or even a pure active substance may be employed.
To manufacture solutions, it is possible to employ solvents, especially alcohols, for example ethyl alcohol or isopropyl alcohol, ketones, such as acetone or cyclohexanone, aliphatic hydrocarbons, such as kerosene, and cyclic hydrocarbons, such as benzene, toluene, xylene, tetrahydronaphthalene and alkylated naphthalenes, and also chlorinated hydrocarbons, such as tetrachloroethane, ethylene chloride, and finally also mineral and vegetable oils or mixtures of the above mentioned substances.
Aqueous preparations are preferably dispersions. The compounds of formula (I) and the active substance, as such or in one of the above mentioned solvents, are homogenised in water, preferably by means of wetting agents or dispersing agents. Amongst cationic dispersing agents, quaternary ammonium compounds may be mentioned as an example, and amongst anionic dispersing agents, soaps, aliphatic long-chain sulphuric acid monoesters, aliphatic-aromatic sulphonic acids and long-chain alkoxyacetic acids may for example be mentioned; amongst non-ionic dispersing agents, polyglycol ethers of fatty alcohols or ethylene oxide condensation products with p-tert. alkylphenols may be mentioned. On the other hand, it is also possible to manufacture concentrates consisting of active substance, synergistic agent or dispersing agent and optionally solvents. Such concentrates can be diluted before use, for example with water.
Dusting agents can be manufactured by mixing or conjoint grinding of the active substance and the synergistic agent with a solid carrier. Possible carriers are for example: talc, diatomaceous earth, kaolin, bentonite, calcium carbonate, boric acid or tricalcium phosphate, but also wood flour, cork powder, charcoal and other materials of vegetable origin. The substances can also be absorbed on the carriers by means of a volatile solvent. Pulverulent preparations and pastes can be rendered capable of suspension in water, and usable as spraying agents, by the addition of wetting agents and protective colloids.
In many cases the use of granules for uniformly releasing the active substance-synergistic agent combinations over a longer period of time is of advantage. These granules can be manufactured by dissolving the active substance in an organic solvent, absorbing this solution by a granular mineral, for example attapulgite or SiO 2 , and removing the solvent. They can also be manufactured by mixing the active substances of formula I with polymerisable compounds, after which a polymerisation is carried out which leaves the active substances unaffected, with the granulation being carried out whilst the polymerisation is still proceeding.
The following Examples illustrate the invention.
EXAMPLE 1
Manufacture of N-o-nitrophenylpropargyl-carbamate
41 of o-nitrophenylisocyanate in 75 ml of dimethylformamide were added dropwise to 14 g of propargyl alcohol in 75 ml of dimethylformamide, at 25°C, whilst cooling. The reaction mixture was stirred at room temperature for approx.
10 to 12 hours and subsequently poured into ice water. The crystals of the compound of formula ##SPC7##
which precipitated were recrystallised from benzene/petroleum ether. Melting point 77°-79°C.
The following compounds of formula ##SPC8##
were also manufactured analogously:
Active substance No. Y 1 Y 2 Y 3 y 4 Y 5 X 1 X 2 Melting point/boiling point ____________________________________________________________ ______________ °C 2 Br H H H H H H 58-59 3 H Br H H H H H 58- 59 4 H H Br H H H H 144-145 5 H H Br H H CH 3 H 114-116 6 Cl H H H H H H 45 7 H H Cl H H H H 49 8 H H Cl H H CH 3 H 100- 102 9 Cl Cl H H H H H 72-73 10 Cl Cl H H H CH 3 H 75-76 11 Cl Cl H H H CH 3 CH 3 83-85 12 Cl H H Cl H H H 71-73 13 Cl H H Cl H CH 3 H 87-88 14 Cl H H Cl H CH 3 CH 3 102-104 15 H Cl H Cl H H H 111-113 16 H Cl H Cl H CH 3 CH 3 104-106 17 H Cl Cl H H H H 78-80 18 H Cl Cl H H CH 3 H 84-85 19 H Cl Cl H H CH 3 CH 3 111-112 20 Cl H Cl Cl H H H 101-103 21 H CF 3 Cl H H H H 77-79 22 H CH 3 Cl H H CH 3 CH 3 103-105 23 H H NO 2 H H H H 174-177 24 NO 2 H Cl H H H H 84-87 25 NO 2 H H Cl H H H 62-64 26 OCH 3 H H H H H H 65-66 27 CH 3 H SCN CH 3 H H H 109-111 28 H CH 3 SCN H H H H 92-93 29 H CF 3 OCH 3 H H H H 78-81 30 H H H H H H H 92-94 31 H Cl H H H CH 3 CH 3 88-93 32 Cl H H H H CH 3 CH 3 47-50 33 H H H H H CH 3 CH 3 102-103 34 H H Cl H H CH 3 CH 3 117-119 35 H Cl H H H CH 3 C 2 H 5 68-72 36 Cl H H H H CH 3 C 2 H 5 108-111/0.06 mm Hg 37 H H Cl H H CH 3 C 2 H 5 63-65 38 H CF 3 H H H CH 3 C 2 H 5 57-58 39 H H H H H CH 3 C 2 H 5 68-69 40 H CF 3 H CF 3 H H H 30-35 41 H CF 3 H CF 3 H CH 3 CH 3 128-130 42 H H CF 3 H H H H 98-99 43 H H CF 3 H H CH 3 H 75-78 44 H H CF 3 H H CH 3 CH 3 107-109 45 H CF 3 H H H H H Oil 46 H CF 3 H H H CH 3 CH 3 84-85 47 H H Br H H CH 3 CH 3 115-117 48 H H CH 3 H H H H 88-90 49 H CH 3 H H H H H 52-54 50 H CH 3 H H H CH 3 CH 3 47-48.5 51 CH 3 H H H H H H 42-44 52 CH 3 H H H H CH 3 CH 3 90-92 53 H H F H H H H 98-99 54 CH 3 H Cl H H H H 79-80 55 CH 3 Cl H H H H H 97-98 56 CH 3 Cl H H H CH 3 CH 3 125-127 57 CH 3 H H CH 3 H H H 105-107 58 CH 3 H CH 3 H H H H 79-80 59 CH 3 H CH 3 H H CH 3 H 73-75 60 OCH 3 H OCH 3 Cl H H H 109-111 61 OCH 3 H H Cl H H H 93-95 62 F H H H H H H Oil 63 H Cl H H H H H 46-47 64 H Cl H H H CH 3 H Oil 65 OCH 3 H NO 2 H H H H 146-148 66 CH 3 H NO 2 Cl H H H 135-138 67 CH 3 CH 3 H H H H H 68-69 68 CH 3 CH 3 H H H CH 3 H 72-73 69 CH 3 CH 3 H H H CH 3 CH 3 104-106 70 H Cl OCH 3 H H H H 79-80 71 OCH 3 H Cl OCH 3 H H H 108-109 72 OCH 3 H OCH 3 H H H H 58-60 73 OCH 3 H H OCH 3 H H H 55 74 CH 3 H H Cl H H H 81-82 75 CH 3 H H H CH 3 H H 103-104 76 CH 3 H H H CH 3 CH 3 H 83-85 77 CH 3 H H H CH 3 CH 3 CH 3 106-108 78 Cl H H CF 3 H H H 57-58 79 H Cl CF 3 H H H H Oil 80 H Cl CF 3 H H CH 3 H 82-84 81 H Cl CF 3 H H CH 3 CH 3 98-99 82 H Cl CH 3 H H H H 83-85 83 H Cl CH 3 H H CH 3 H 60-62 84 H Cl CH 3 H H CH 3 CH 3 86-87 85 H Br OCH 3 Br H H H 115-116 ____________________________________________________________ ______________
EXAMPLE 2
Dusting Agents
Equal parts of a mixture of active substance and synergistic agent and of precipitated silica are finely ground. Dusting agents, preferably containing 1-6 percent of active substance, can be manufactured therefrom by mixing with kaolin or talc.
Spraying Powder
To manufacture a spraying powder, the following components are for example mixed and finely ground:
50 parts of a mixture of active substance and synergistic agent
20 parts of highly adsorbent silica
25 parts of Bolus alba (Kaolin)
1.5 parts of sodium 1-benzyl-2-stearyl-benzimidazole-6,3'-disulphonate and
3.5 parts of a reaction product of p-tert. octylphenol and ethylene oxide.
Emulsion Concentrate
The easily soluble mixture of active substance and synergistic agent can also be formulated as an emulsion concentrate in accordance with the following instruction:
20 parts of a mixture of active substance and synergistic agent,
70 parts of xylene and
10 parts of a mixture of a reaction product of an alkyl phenol with ethylene oxide and calcium dodecylbenzenesulphonate are mixed. On dilution with water to the desired concentration, a sprayable emulsion results.
Granules
7.5 g of a mixture of active substance and synergistic agent are dissolved in 100 ml of acetone and the acetone solution thus obtained is added to 92 g of granular attapulgite. The whole is well mixed and the solvent is stripped off in a rotary evaporator. Granules containing 7.5 percent of active substance are obtained.
EXAMPLE 3
Test for Synergistic Action
For this test, female house flies aged from 2 to 5 days were used. Before the start of the test, the flies were sorted as to gender under CO 2 narcosis, and the females were placed in groups of 10. The flies, which were kept motionless with CO 2 , were treated with a dispenser which on pressing the button each time releases 1 microlitre of the solution of the test substance in acetone. After the treatment, the flies were placed in groups of 10 in Petri dishes into which a cottonwool pad impregnated with honey water had been introduced for the flies to feed on. After 24 hours the test was evaluated by counting the flies which could no longer move. The results quoted in the table represent average values of the percentage destruction from four repeat tests.
The following were each used per fly (weight of one fly 20 mg (average value)):
a. 0.08γ of each of the compounds Nos. 1, 2, 3, 6, 7, 9, 12, 15, 20, 45, 49, 53, 55, 57 and 78
b. 0.08γ of the compound of formula ##SPC9##
c. 0.08γ of compound (A) and 0.08γ of compounds Nos. 1, 2, 3, 6, 7, 9, 12, 15, 20, 45, 49, 53, 55, 57 and 78.
______________________________________ Compound No. 0.08γ of synergistic agent 0.08γ of (A) 0.08γ of A and 0.08γ of synergistic agent ______________________________________ 1 17 92 2 0 17 65 3 0 17 50 6 0 17 90 7 0 17 40 9 0 17 95 12 0 17 95 15 0 17 45 20 0 17 60 45 0 17 80 49 0 17 65 53 0 17 65 55 0 17 90 57 0 17 45 78 0 17 75 ______________________________________ EXAMPLE 4
A test of the synergistic action of the compound No. 1 on the compounds of formulae ##SPC10##
The results listed in the table represent average values of the percentage destruction of female house flies, from two repeat experiments.
______________________________________ a. 0.32γ Compound No. 1 0 0.32γ (A) 5 0.32γ Compound No. 1 + 0.32γ (A) 84 b. 0.08γ Compound No. 1 0 0.08γ (B) 5 0.08γ Compound No. 1 + 0.08γ (B) 95 c. 0.1γ Compound No. 1 0 0.1γ (C) 3 0.1γ Compound No. 1 + 0.1γ (C) 80 d. 0.2γ Compound No. 1 0 0.2γ (D) 10 0.2γ Compound No. 1+ 0.2γ (D) 99 e. 0.08γ Compound No. 1 0 0.08γ (E) 15 0.08γ Compound No. 1 + 0.08γ (E) 88 f. 0.6γ Compound No. 1 0 0.6γ (F) 15 0.6γ Compound No. 1 + 0.6γ (F) 73 g. 0.1γ Compound No. 1 0 0.1γ (G) 3 0.1γ Compound No. 1 + 0.1γ (G) 78 h. 0.1γ Compound No. 1 0 0.1γ (H) 15 0.1γ Compound No. 1+ 0.1γ (H) 99 i. 0.07γ Compound No. 1 0 0.07γ (I) 10 0.07γ Compound No. 1 + 0.07γ (I) 29 ______________________________________
The compounds which are used as synergistic agents according to the present invention have the formula ##SPC2##
In which R 1 , R 2 and R 3 , which may be the same or different, each represents a hydrogen atom or a halogen atom or an alkyl, alkoxy or halogenalkyl radical each having from one to four carbon atoms or a --NO 2 or --SCN group, and R 4 and R 5 , which may be the same or different, each represents a hydrogen atom or an alkyl group having from one to four carbon atoms.
The alkyl and alkoxy groups which are represented by R 1 , R 2 , R 3 , R 4 and R 5 , may be substituted or unsubstituted, branched or straight-chained. Suitable alkyl and alkoxy groups are, for example, methyl, ethyl and methoxy groups.
Compounds of special importance are those of the formulae ##SPC3##
In each of which R 6 , R 7 and R 8 , which may be the same or different, each represents a hydrogen, fluorine, chlorine or bromine atom or a methyl, methoxy, --CF 3 . --NO 2 or --SCN group.
An especially suitable compound is that of the formula ##SPC4##
This compound is new and therefore also forms a subject of the invention.
The compounds of the formula I may be prepared according to methods which are, in themselves, known, for example, by the reaction of an isocyanate of the formula ##SPC5##
With an alcohol of the formula ##SPC6##
In an inert solvent, for example, benzene, petroleum ether or dimethylformamide, the substituents R 1 , R 2 , R 3 , R 4 and R 5 having the same meanings as those specified for formula I.
The compounds defined by the general formula I are capable of increasing the activity of insecticidal and/or acaricidal compounds many-fold (synergism). Surprisingly, it has also been found that when using compounds of the formula I, insects or representatives of the order Acarina, which are resistant to carbamates or phosphoric acid esters, can be rendered completely sensitive to these latter compounds. Suitable insecticidally or acaricidally active substances are, for example, the following compounds:
PHOSPHORIC ACID DERIVATIVES
Bis-O,O-diethylphosphoric acid anhydride (TEPP)
O,O,O,O-Tetrapropyldithiopyrophosphate
Dimethyl(2,2,2-trichloro-1-hydroxyethyl)phosphonate (TRICHRORFON)
1,2-Dibromo-1,2-dichlorethyldimethylphosphate (NALED)
2,2-Dichlorovinyldimethylphosphate (DICHLORFOS)
2-Methoxycarbamyl-1-methylvinyldimethylphosphate (MEVINPHOS)
Dimethyl-1-methyl-2-(methylcarbamoyl)vinylphosphate cis (MONOCROTOPHOS)
3-(Dimethoxyphosphinyloxy)-N-methyl-N-methoxy-cis-croton -amide
3-(Dimethoxyphosphinyloxy)-N,N-dimethyl-cis-crotonamide (DICROTOPHOS)
2-Chloro-2-diethylcarbamoyl-1-methylvinyldimethylphospha te (PHOSPHAMIDON)
O,O-Diethyl-O-2-(ethylthio)-ethylthiophosphate (DEMETON)
O,O-Diethyl-S-2-(ethylthio)-ethylthiophosphate
S-Ethylthioethyl-O,O-dimethyl-dithiophosphate (THIOMETON)
O,O-Diethyl-S-ethylmercaptomethyldithiophosphate (PHORATE)
O,O-Diethyl-S-2-[(ethylthio)ethyl]dithiophosphate (DISULFOTON)
O,O-Dimethyl-S-2-(ethylsulphinyl)ethylthiophosphate (OXYDEMETONMETHYL)
O,O-Dimethyl-S-(1,2-dicarbethoxyethyl)dithiophosphate (MALATHION)
(O,O,O,O-Tetraethyl-S,S'-methylene-bis-[dithiophosphate] (ETHION)
O-Ethyl-S,S-dipropyldithiophosphate
O,O-Dimethyl-S-(N-methyl-N-formylcarbamoylmethyl)-dithio phosphate (FORMOTION)
S-N-(1-Cyano-1-methylethyl)carbamoylmethyldiethylthiolph osphate (CYANTHOAT)
S-(2-Acetamidoethyl)-O,O-dimethyldithiophosphate
Hexamethylphosphoric acid triamide (HEMPA)
O,O-Dimethyl-O-p-nitrophenylthiophosphate (PARATHION-METHYL)
O,O-Diethyl-O-p-nitrophenylthiophosphate (PARATHION)
O-Ethyl-O-p-nitrophenylthiophosphonate (EPN)
O,O-Dimethyl-O-(4-nitro-m-tolyl)thiophosphate (FENITROTHION)
O,O-Dimethyl-O-(2-chloro-4-nitrophenyl)thiophosphate (DICAPTHON)
O,O-Dimethyl-O-p-cyanophenylthiophosphate (CYANOX)
O-Ethyl-O-p-cyanophenylphenylthiophosphonate
O,O-Diethyl-O-2,4-dichlorophenylthiophosphate (DICHROFENTHION)
O-2,4-Dichlorophenyl-O-methylisopropylamidothiophosphate
O,O-Dimethyl-O-2,4,5-trichlorophenylthiophosphate (RONNEL)
O-Ethyl-O-2,4,5-trichlorophenylethylthiophosphonate (TRICHLORONAT)
O,O-Dimethyl-O-2,5-dichloro-4-bromophenylthiophosphate (BROMOPHOS)
O,O-Diethyl-O-2,5-dichloro-4-bromophenylthiophosphate (BROMOPHOS-ETHYL)
4-tert. Butyl-2-chlorophenyl-N-methyl-O-methylamidophosphate (CRUFOMAT)
Dimethyl-p-(methylthio)phenylphosphate
O,O-Dimethyl-O-(3-methyl-4-methylmercaptophenyl)thiophos phate (FENTHION)
Isopropylamino-O-ethyl-O-(4-Methylmercapto-3-methylpheny l)phosphate
O,O-Diethyl-O-p-[(methylsulphinyl)phenyl]-thiophosphate (FENSULFOTHION)
O,O-Dimethyl-O-p-sulphamidophenylthiophosphate
O-[p-(Dimethylsulphamido)phenyl]O,O-dimethylthiophosphat e (FAMPHUR)
O,O,O',O' -Tetramethyl-O,O'-thiodi-p-phenylenethiophosphate
O-(p-(p-Chlorophenylazophenyl)O,O-dimethylthiophosphate (AZOTHOAT)
O-Ethyl-S-phenyl-ethyldithiophosphonate
O-Ethyl-S-4-chlorophenyl-ethyldithiophosphonate
O-Isobutyl-S-p-chlorophenyl-ethyldithiophosphonate
O,O-Dimethyl-S-p-chlorophenylthiophosphate
O,O-Dimethyl-S-(p-chlorophenylthiomethyl)-dithiophosphat e
O,O-Diethyl-p-chlorophenylmercaptomethyl-dithiophosphate (CARBONPHENOTHION)
O,O-Diethyl-S-p-chlorophenylthiomethyl-thiophosphate
O,O-Dimethyl-S-(carbethoxy-phenylmethyl)dithiophosphate (PHENOTHOAT)
O,O-Diethyl-S-(carbofluorethoxy-phenylmethyl)-dithiophos phate
O,O-Dimethyl-S-(carbisopropoxy-phenylmethyl)-dithiophosp hate
O,O-Dimethyl-O-(alpha-methylbenzyl-3-hydroxycrotonyl)pho sphate,
2-Chloro-1-(2,4-dichlorophenyl)vinyl-diethylphosphate (CHLORFENVINPHOS)
2-Chloro-1-(2,4,5-trichlorophenyl)vinyl-dimethylphosphat e
O-(2-Chloro-1-(2,5-dichlorophenyl)vinyl)-O,O-diethylthio phosphate
Phenylglyoxylonitriloxime-O,O-diethylthiophosphate (PHOXIM)
O,O-Diethyl-O-(3-chloro-4-methyl-2-oxo-2-H-1-benzopyran- 7-yl)-thiophosphate (COUMAPHOS)
O,O-Diethyl-7-hydroxy-3,4-tetramethylene-coumarinyl-thio phosphate (COUMITHOAT)
2,3-p-Dioxanedithiol-S,S-bis(O,O-diethyldithiophosphate) (DIOXATHION)
2-Methoxy-4-H-1,3,2-benzodioxaphosphorine-2-sulphide
O,O-Diethyl-O-(5-phenyl-3-isooxyzolyl (sic)) thiophosphate
S-[(6-Chlor-2-oxo-3-benzoxazolinyl)methyl]O,O-diethyldit hiophosphate (PHOSALON)
2-(Diethoxyphosphinylimino)-4-methyl-2,3-dithiolane
O,O-Dimethyl-S-[2-methoxy-1,3,4-thiadiazol-5-(4H)-onyl-( 4)-methyl]dithiopho sphate
Tris-(2-methyl-1-aziridinyl)-phosphine-oxide (METEPA)
O,O-Dimethyl-S-phthalimidomethyl-dithiophosphate
S-(2 -Chloro-1-phthalimidoethyl)-O,O-diethyldithiophosphate
N-Hydroxynaphthalimido-diethylphosphate
Dimethyl-3,5,6-trichloro-2-pyridylphosphate
O,O-Dimethyl-O-(3,5,6-trichloro-2-pyridyl)thiophosphate
O,O-Diethyl-O-(3,5,6-trichloro-2-pyridyl)thiophosphate
O,O-Diethyl-O-2-pyrazinylthiophosphate (THIONAZIN) O,O-Diethyl-O-(2-quinoxylyl)thiophosphate
O,O-Dimethyl-S-(4-oxo-1,2,3-benzotriazin-3(4H)-ylmethyl) dithiophosphate (AZINPHOSMETHYL)
O,O-Diethyl-S-(4-oxo-1,2,3-benzotriazin-3(4H)-ylmethyl)d ithiophosphate (AZINPHOSETHYL)
S-[(4,6-Diamino-s-triazin-2-yl)methyl]-O,O-dimethyldithi ophosphate (MENAZON)
S-[2-(Ethylsulphonyl)ethyl]dimethylthiophosphate (DIOXYDEMETON-S-METHYL)
Diethyl-S-[2-(ethylsulphinyl)ethyl]dithiophosphate (OXYDISULFOTON)
Bis-O,O-diethylthiophosphoric acid anhydride (SULFOTEP)
Dimethyl-1,3-di(carbomethoxy)-1-propen-2-yl-phosphate
Dimethyl-(2,2,2-trichloro-1-butyroyloxyethyl)phosphonate (BUTONAT)
O,O-Dimethyl-O-(2,2-dichloro-1-methoxy-vinyl)phosphate
O,o-dimethyl-O-(3-chloro-4-nitrophenyl)thiophosphate (CHLORTHION)
O,O-Dimethyl-O(or S)-2-(ethylthioethyl)thiophosphate (DEMETONS-METHYL)
Bis-(dimethylamido)fluorophosphate (DIMEFOX)
2-(O,O-Dimethyl-phosphoryl-thiomethyl)-5-methoxy-pyrone- 4
3,4-Dichlorobenzyl-triphenylphosphonium chloride
Dimethyl-N-methoxymethylcarbamoylmethyl-dithiophosphate (FORMOCARBAM)
O,O-Diethyl-O-(2,2-dichloro-1-chlorethoxyvinyl)phosphate
O,O-Dimethyl-O-(2,2-dichloro-1-chlorethoxyvinyl)phosphat e
O-Ethyl-S,S-diphenyldithiolphosphate
O-Ethyl-S-benzyl-phenyldithiophosphonate
O,O-Diethyl-S-benzyl-thiophosphate
O,O-Dimethyl-S-(4-chlorophenylthiomethyl)dithiophosphate (METHYLCARBOPHENOTHION)
O,O-Dimethyl-S-(ethylthiomethyl)dithiophosphate
Diisopropylaminofluorophosphate (MIPAFOX)
O,O-Dimethyl-S-(morpholinylcarbamoylmethyl)dithiophospha te (MORPHOTHION)
Bismethylamido-phenylphosphate
O,O-Dimethyl-S-(benzenesulphonyl)dithiophosphate
O,O-Dimethyl-(S and O)-ethylsulphinylethylthiophosphate
O,O-Diethyl-O-4-nitrophenylphosphate
O,O-Diethyl-S-( 2,5-dichlorophenylthiomethyl)dithiophosphate (PHENDAPTON)
Triethoxy-isopropoxy-bis (thiophosphinyl)disulphide
O,O-Diethyl -O-(4-methyl-coumarinyl-7)-thiophosphate (POTASAN)
2-Methoxy-4H-1,3,2-benzodioxaphosphorine-2-oxide
Octamethylpyrophosphoramide (SCHRADAN)
Bis(dimethoxythiophosphinylsulphido)-phenylmethane
5-Amino-bis(dimethylamido)phosphinyl-3-phenyl-1,2,4-tria zole (TRIAMIPHOS)
N-Methyl-5-(O,O-dimethylthiolphosphoryl)-3-thiavaleramid e (VAMIDOTHION) and
N,N,N' ,N'-Tetramethyldiamidofluorophosphate (DIMEFOX)
CARBAMIC ACID DERIVATIVES
1-Naphthyl-N-methylcarbamate (CARBARYL)
2-Butinyl-4-chlorophenylcarbamate
4-Dimethylamino-3,5-xylyl-N-methylcarbamate
4-Dimethylamino-3-tolyl-N-methylcarbamate (AMINOCARB)
3,4,5-Trimethylphenyl-N-methylcarbamate
2-Chlorophenyl-N-methylcarbamate (CPMC)
5-Chlor-6-oxo-2-norbornane-carbonitrile-O-(methylcarbamo yl)-oxime
1-(Dimethylcarbamoyl)-5-methyl-3-pyrazolyl-N,N-dimethylc arbamate (DIMETILAN)
2,3-Dihydro-2,2-dimethyl-7-benzofuranyl-N-methylcarbamat e (CARBOFURAN)
2-Methyl-2-methylthio-propionaldehyde-O-(methylcarbamoyl )oxime (ALDICARB)
8-Quinaldyl-N-methylcarbamate and its salts
Methyl 2-isopropyl-4-(methylcarbamoyloxy)carbanilate
m-(1-Ethylpropyl)phenyl-N-methylcarbamate
3,5-Di-tert.butyl-N-methylcarbamate
m-(1-Methylbutyl)phenyl-N-methylcarbamate
2-Isopropylphenyl-N-methylcarbamate
2-sec.Butylphenyl-N-methylcarbamate
m-Tolyl-N-methylcarbamate
2,3-Xylyl-N-methylcarbamate
3-Isopropylphenyl-N-methylcarbamate
3-tert.Butylphenyl-N-methylcarbamate
3-sec.-Butylphenyl-N-methylcarbamate
3-Isopropyl-5-methylphenyl-N-methylcarbamate (PROMECARB)
3,5-Diisopropylphenyl-N-methylcarbamate
2-Chlor-5-isopropylphenyl-N-methylcarbamate
2-Chloro-4,5-dimethylphenyl-N-methylcarbamate
2-(1,3-Dioxolan-2-yl)phenyl-N-methylcarbamate (DIOXYCARB)
2-(4,5-Dimethyl-1,3-dioxolan-2-yl)phenyl-N-methylcarbama te
2-(1,3-Dioxan-2-yl)phenyl-N-methylcarbamate
2-(1,3-Dithiolan-2-yl)phenyl-N-methylcarbamate
2-(1,3-Dithiolan-2-yl)phenyl-N,N-dimethylcarbamate
2-Isopropoxyphenyl-N-methylcarbamate (ARPROCARB)
2-(2-Propinyloxy)phenyl-N-methylcarbamate
2-(2-Propinyloxy)phenyl-N-methylcarbamate
3-(2-Propinyloxy)phenyl-N-methylcarbamate
2-Dimethylaminophenyl-N-methylcarbamate
2-Diallylaminophenyl-N-methylcarbamate
4-Diallylamino-3,5-xylyl-N-methylcarbamate (ALLYXICARB)
4-Benzothienyl-N-methylcarbamate
2,3-Dihydro-2-methyl-7-benzofuranyl-N-methylcarbamate
3-Methyl-1-phenylpyrazol-5-yl-N,N-dimethylcarbamate
1-Isopropyl-3-methylpyrazol-5-yl-N,N-dimethylcarbamate (ISOLAN)
2-(N',N'-Dimethylcarbamoyl)-3-methylpyrazol-5-yl-N,N-dim ethylcarbamate
2-Dimethylamino-5,6-dimethylpyrimidin-4-yl-N,N-dimethylc arbamate
3-Methyl-4-dimethylaminomethyleneiminophenyl-N-methylcar bamate
3-Dimethylamino-methyleneiminophenyl-N-methylcarbamate
1-Methylthio-ethylimino-N-methylcarbamate (METHOXYMYL)
2-Methylcarbamoyloxyimino-1,3-dithiolane
5-Methyl-2-methylcarbamoyloxyimino- 1,3-oxathiolane
2-(1-Methoxy-2-propoxy)phenyl-N-methylcarbamate
2-(1-Butin-3-yl-oxy)phenyl-N-methylcarbamate
3-Methyl-4 -(dimethylamino-methylmercapto-methyleneimino)phenyl-N-methy lcarbamate
1,3-Bis(carbamoylthio)-2-(N,N-dimethylamino)-propane hydrochloride
5,5-Dimethylhydroresorcinoldimethylcarbamate
2-[Propargylethylamino]-phenyl-N-methylcarbamate
2-[Propargylmethylamino]-phenyl-N-methylcarbamate
2-[Dipropargylamino]-phenyl-N-methylcarbamate
3-Methyl-4-[dipropargylamino]-phenyl-N-methylcarbamate
3,5-Dimethyl-4-[dipropargylamino]-phenyl-N-methylcarbama te
2-[Allyl-isopropylamino]-phenyl-N-methylcarbamate and
3-[Allyl-isopropylamino]-phenyl-N-methylcarbamate.
Chlorinated Hydrocarbons
γ-Hexachlorocyclohexane [Gammerxane; Lindane; γ HCH]
1,2,4,5,6,7,8,8-Octachloro-3α,4,7,7α '-tetrahydro-4,7-methyleneindane [Chlordan]
1,4,5,6,7,8,8-Heptachloro-3α ,4,7,7α -tetrahydro-4,7-methyleneindane [Heptachlor]
1,2,3,4,10,10-Hexachloro-1,4,4α ,5,8,8α-hexahydro-endo-1,4-exo-5,8-dimethanonaphthalene [Aldrin]
1,2,3,4,10,10-Hexachloro-6,7-epoxy-1,4,4α ,5,6,7,8,8α-octahydro-exo-1,4-endo-5,8-dimethanonaphthalene [Dieldrin]
ditto, endo-endo- [Endrin]
6,7,8,9,10,10-Hexachloro-1,5,5α,6,9,9α-hexahydro-6,9-m ethano-2, 3,4 benzo [e]-dioxa-thiepene-3-oxide [Endosulfan]
Chlorinated camphor [Toxaphen] Decachloroctahydro-1,3,4-metheno-2H-cyclobuta[ e d] pentalen-2-one
Dodecachloroctahydro-1,3,4-metheno-1H-cyclobuta[ c d] pentalene [Mirex]
Ethyl-1,1α ,3,3α ,4,5,5,5α ,5α,6-decachloroctahydro-2-hydroxy-1,3,4-metheno-1H-cyclobu ta[ c d] pentalene-2- laevulinate
Bis(pentachloro-2,4-cyclopentadien-1-yl)
Dinoctone
1,1,1-Trichloro-2,2 -bis(p-chlorophenyl)ethane [DDT]
Dichlorodiphenyl-dichloroethane [TDE]
Di(p-chlorophenyl)-trichloromethylcarbinol [Dicofol]
Ethyl-4,4'-dichlorophenylglycollate [Chlorobenzylate]
Ethyl-4,4'-dibromobenzylate [Bromobenzylate]
Isopropyl-4,4'-dichlorobenzylate
1,1,1-Trichloro-2,2 bis(p-methoxyphenyl)ethane [Methoxychlor]
Diethyl-diphenyl-dichloroethane
Decachloropentacyclo( 3,3,2, O 2 ,6, O 3 ,9, O 7 ,10 )decan-4-one [Chlordecon].
NITROPHENOLS AND DERIVATIVES
4,6-Dinitro-6-methylphenol Na salt [dinitrocresol]
Dinitrobutylphenol-2,2',2"-triethanolamine salt
2-Cyclohexyl-4,6-dinitrophenol [Dinex]
2-(1-Methylheptyl)-4,6-dinitrophenyl-crotonate [Dinocap]
2 sec.-Butyl-4,6-dinitrophenyl-3-methyl-butenoate [Binapacryl]
2 sec.-Butyl-4,6-dinitrophenyl-cyclopropionate and
2 sec.-Butyl-4,6-dinitrophenyl-isopropyl-carbonate [Dinobuton]
VARIOUS SUBSTANCES
Sabadilla
Rotenone
Cevadine
Veratridine
Ryania
Pyrethrin
3-Allyl-2-methyl-4-oxo-2-cyclopenten-1-yl-chrysanthemuma te (Allethrin)
6-Chloropiperonyl-chrysanthemumate (Barthrin)
2,4-Dimethylbenzyl-chrysanthemumate (Dimethrin)
2,3,4,5-Tetrahydrophthalimidomethyl-chrysanthemumate
(5-Benzyl-3-furyl)-methyl-2,2-dimethyl-3-(2-methylpropan yl)cyclopropanecarb oxylate
Nicotine
Bacillus thuringiensis Berliner
Dicyclohexylcarbodiimide
Diphenyldiimide [azobenzene (sic)]
4-Chlorobenzyl-4-chlorophenylsulphide [Chlorobenside]
Creosote oil
6-Methyl-2-oxo-1,3-dithiolo-[4,5-b]-quinoxaline [Quinomethionate]
(I)-3-(2-Furfuryl)-2-methyl-4-oxocyclopent-2-enyl(I)-(ci s+trans)chrysanthem um-monocarboxylate [Furethrin]
2-Pivaloyl-indane-1,3-dione [Pindon]
2-Fluorethyl(4-bisphenyl)acetate
2-Fluoro-N-methyl-N(1-naphthyl)-acetamide
Pentachlorophenol and salts
2,2,2-Trichloro-N-(pentachlorophenyl)-acetimidoyl chloride
N'-(4-Chloro-2-methylphenyl)-N,N-dimethylformamidine (Chlorphenamidine)
4-Chlorobenzyl-4-fluorophenyl-sulphide (Fluorobenside)
5,6-Dichloro-1-phenoxycarbanyl-2-trifluoromethyl-benzimi dazole (Fenozaflor)
Tricyclohexyl-stannic-hydroxide
2-Thiocyanatoethyl-lauric acid ester
β-Butoxy-β'-thiocyanatodiethyl-ether
Isobornyl-thiocyanatoacetate
p-Chlorophenyl-p-chlorobenzenesulphonate (Ovex)
2,4-Dichlorophenyl-benzenesulphonate
p-Chlorophenyl-benzenesulphonate (Fenson)
p-Chlorphenyl-2,4,5-trichlorophenylsulphone (Tetradifon)
p-Chlorophenyl-2,4,5-trichlorophenylsulphide (Tetrasul)
Methyl bromide
p-Chlorophenyl-phenylsulphone
p-Chlorobenzyl-p-chlorophenylsulphide (Chlorobenside)
4-Chlorophenyl-2,4,5-trichlorophenylazosulphide
2(p-tert.-Butylphenoxy)-1-methylethyl-2-chloroethyl-sulp hite
2(p-tert.-Butylphenoxy)cyclohexyl-2-propinyl-sulphite
4,4'-Dichloro-N-methylbenzenesulphonanilide
N-(2-Fluoro-1,1,2,2-tetrachloroethylthio)-methanesulphon anilide
2-Thio-1,3-dithiolo-(4,5-6)quinoxaline (Thioquinox)
Chloromethyl-p-chlorophenylsulphone (lauseto (sic!) new)
1,3,6,8-Tetranitrocarbazole and
Prop-2-ynyl-(4-t-butylphenoxy)-cyclohexylsulphite (Propargil).
The ratio of the insecticidally and/or acaricidally active substance to the compounds of the formula I is preferably within the range of from 0.01:10 to 200:1.
Such synergistically active mixtures can preferentially be employed against all harmful insects, for example against aphids, such as the green peach aphid (Myzus persicae), and the black bean aphid (Doralis fabae); scale insects lice such as Aspidiotus hederae, Lecanium hesperidium, Pseudococcus maritimus; Thysanoptera such as Hercinothrios femoralis, and bugs such as the beet bug (Piesma quadrata) or the bed bug (Cimex lectularius), caterpillars, such as Plutella maculipennis and Lymantria dispar; weevils such as the granary weevil (Calandra granaria) or the Colorado beetle (Leptinotarsa decemlineata), but also varieties which live in soil, such as wireworms (Agriotes sp.) or cockchafer grubs (Melolontha melolontha); cockroaches, such as the German cockroach (Blattella germanica); Orthoptera, such as the cricket (Gryllus domesticus); termites, such as Beticulitermes; Hymenoptera, such as ants; Diptera, such as the vinegar fly (Drosophila melanogaster), the Mediterranean fruit fly (Ceratitis capitata), the housefly (Musca domestica), and gnats, such as the yellow fever mosquito (Aedes aegypti).
The use of this synergistic mixture is also especially effective in combatting representatives of the order Acarina such as for example Eulaelaps, Echinolaelaps, Laelaps, Haemogamasus, Dermanyssus, Ornithonyssus, Allodermanyssus, in particular Allodermanyssus sanguineus, Pneumonyssus, Amblyomma, Aponomma, Boophilus, Dermacentor, Haemophysalis, Hyalomma, Ixodes, Margaropus, Rhipicephalus, Ornithodorus; Octobius, Cheyletidae, for example Cheyletus, Psorergates, Demodicidae, Trombiculidae, for example Trombicula, Eutrombicula, Schongastia, Acomatacurus, Neoschongastia, Euschongastia, Sarcoptiformes for example Notoedres, Sarcoptes, Knemidokoptes, Psoroptidae, for example Psoroptes, Chorioptes, otodectes or Tetranychidae, for example Tetranychus telarius; Tetranychus urticae and the like.
The mixtures can either be used by themselves or together with suitable carriers and/or additives.
Suitable carriers and additives can be solid or liquid and correspond to the substances which are customary in formulation technology, for example, natural or regenerated mineral substances, solvents, dispersing agents, wetting agents, adhesives, thickeners, binders or fertilisers.
Such preparations can be employed in the form of solutions, emulsions, suspensions, granules or dusting agents. The methods of application depend on the end uses and must ensure that the active substance can be finely distributed.
The content of active substance in the preparations described above is between 0.1 and 95 percent. At the same time it should be mentioned that in the case of application from aircraft or by means of other suitable application instruments, concentrations of up to 99.5 percent or even a pure active substance may be employed.
To manufacture solutions, it is possible to employ solvents, especially alcohols, for example ethyl alcohol or isopropyl alcohol, ketones, such as acetone or cyclohexanone, aliphatic hydrocarbons, such as kerosene, and cyclic hydrocarbons, such as benzene, toluene, xylene, tetrahydronaphthalene and alkylated naphthalenes, and also chlorinated hydrocarbons, such as tetrachloroethane, ethylene chloride, and finally also mineral and vegetable oils or mixtures of the above mentioned substances.
Aqueous preparations are preferably dispersions. The compounds of formula (I) and the active substance, as such or in one of the above mentioned solvents, are homogenised in water, preferably by means of wetting agents or dispersing agents. Amongst cationic dispersing agents, quaternary ammonium compounds may be mentioned as an example, and amongst anionic dispersing agents, soaps, aliphatic long-chain sulphuric acid monoesters, aliphatic-aromatic sulphonic acids and long-chain alkoxyacetic acids may for example be mentioned; amongst non-ionic dispersing agents, polyglycol ethers of fatty alcohols or ethylene oxide condensation products with p-tert. alkylphenols may be mentioned. On the other hand, it is also possible to manufacture concentrates consisting of active substance, synergistic agent or dispersing agent and optionally solvents. Such concentrates can be diluted before use, for example with water.
Dusting agents can be manufactured by mixing or conjoint grinding of the active substance and the synergistic agent with a solid carrier. Possible carriers are for example: talc, diatomaceous earth, kaolin, bentonite, calcium carbonate, boric acid or tricalcium phosphate, but also wood flour, cork powder, charcoal and other materials of vegetable origin. The substances can also be absorbed on the carriers by means of a volatile solvent. Pulverulent preparations and pastes can be rendered capable of suspension in water, and usable as spraying agents, by the addition of wetting agents and protective colloids.
In many cases the use of granules for uniformly releasing the active substance-synergistic agent combinations over a longer period of time is of advantage. These granules can be manufactured by dissolving the active substance in an organic solvent, absorbing this solution by a granular mineral, for example attapulgite or SiO 2 , and removing the solvent. They can also be manufactured by mixing the active substances of formula I with polymerisable compounds, after which a polymerisation is carried out which leaves the active substances unaffected, with the granulation being carried out whilst the polymerisation is still proceeding.
The following Examples illustrate the invention.
EXAMPLE 1
Manufacture of N-o-nitrophenylpropargyl-carbamate
41 of o-nitrophenylisocyanate in 75 ml of dimethylformamide were added dropwise to 14 g of propargyl alcohol in 75 ml of dimethylformamide, at 25°C, whilst cooling. The reaction mixture was stirred at room temperature for approx.
10 to 12 hours and subsequently poured into ice water. The crystals of the compound of formula ##SPC7##
which precipitated were recrystallised from benzene/petroleum ether. Melting point 77°-79°C.
The following compounds of formula ##SPC8##
were also manufactured analogously:
Active substance No. Y 1 Y 2 Y 3 y 4 Y 5 X 1 X 2 Melting point/boiling point ____________________________________________________________ ______________ °C 2 Br H H H H H H 58-59 3 H Br H H H H H 58- 59 4 H H Br H H H H 144-145 5 H H Br H H CH 3 H 114-116 6 Cl H H H H H H 45 7 H H Cl H H H H 49 8 H H Cl H H CH 3 H 100- 102 9 Cl Cl H H H H H 72-73 10 Cl Cl H H H CH 3 H 75-76 11 Cl Cl H H H CH 3 CH 3 83-85 12 Cl H H Cl H H H 71-73 13 Cl H H Cl H CH 3 H 87-88 14 Cl H H Cl H CH 3 CH 3 102-104 15 H Cl H Cl H H H 111-113 16 H Cl H Cl H CH 3 CH 3 104-106 17 H Cl Cl H H H H 78-80 18 H Cl Cl H H CH 3 H 84-85 19 H Cl Cl H H CH 3 CH 3 111-112 20 Cl H Cl Cl H H H 101-103 21 H CF 3 Cl H H H H 77-79 22 H CH 3 Cl H H CH 3 CH 3 103-105 23 H H NO 2 H H H H 174-177 24 NO 2 H Cl H H H H 84-87 25 NO 2 H H Cl H H H 62-64 26 OCH 3 H H H H H H 65-66 27 CH 3 H SCN CH 3 H H H 109-111 28 H CH 3 SCN H H H H 92-93 29 H CF 3 OCH 3 H H H H 78-81 30 H H H H H H H 92-94 31 H Cl H H H CH 3 CH 3 88-93 32 Cl H H H H CH 3 CH 3 47-50 33 H H H H H CH 3 CH 3 102-103 34 H H Cl H H CH 3 CH 3 117-119 35 H Cl H H H CH 3 C 2 H 5 68-72 36 Cl H H H H CH 3 C 2 H 5 108-111/0.06 mm Hg 37 H H Cl H H CH 3 C 2 H 5 63-65 38 H CF 3 H H H CH 3 C 2 H 5 57-58 39 H H H H H CH 3 C 2 H 5 68-69 40 H CF 3 H CF 3 H H H 30-35 41 H CF 3 H CF 3 H CH 3 CH 3 128-130 42 H H CF 3 H H H H 98-99 43 H H CF 3 H H CH 3 H 75-78 44 H H CF 3 H H CH 3 CH 3 107-109 45 H CF 3 H H H H H Oil 46 H CF 3 H H H CH 3 CH 3 84-85 47 H H Br H H CH 3 CH 3 115-117 48 H H CH 3 H H H H 88-90 49 H CH 3 H H H H H 52-54 50 H CH 3 H H H CH 3 CH 3 47-48.5 51 CH 3 H H H H H H 42-44 52 CH 3 H H H H CH 3 CH 3 90-92 53 H H F H H H H 98-99 54 CH 3 H Cl H H H H 79-80 55 CH 3 Cl H H H H H 97-98 56 CH 3 Cl H H H CH 3 CH 3 125-127 57 CH 3 H H CH 3 H H H 105-107 58 CH 3 H CH 3 H H H H 79-80 59 CH 3 H CH 3 H H CH 3 H 73-75 60 OCH 3 H OCH 3 Cl H H H 109-111 61 OCH 3 H H Cl H H H 93-95 62 F H H H H H H Oil 63 H Cl H H H H H 46-47 64 H Cl H H H CH 3 H Oil 65 OCH 3 H NO 2 H H H H 146-148 66 CH 3 H NO 2 Cl H H H 135-138 67 CH 3 CH 3 H H H H H 68-69 68 CH 3 CH 3 H H H CH 3 H 72-73 69 CH 3 CH 3 H H H CH 3 CH 3 104-106 70 H Cl OCH 3 H H H H 79-80 71 OCH 3 H Cl OCH 3 H H H 108-109 72 OCH 3 H OCH 3 H H H H 58-60 73 OCH 3 H H OCH 3 H H H 55 74 CH 3 H H Cl H H H 81-82 75 CH 3 H H H CH 3 H H 103-104 76 CH 3 H H H CH 3 CH 3 H 83-85 77 CH 3 H H H CH 3 CH 3 CH 3 106-108 78 Cl H H CF 3 H H H 57-58 79 H Cl CF 3 H H H H Oil 80 H Cl CF 3 H H CH 3 H 82-84 81 H Cl CF 3 H H CH 3 CH 3 98-99 82 H Cl CH 3 H H H H 83-85 83 H Cl CH 3 H H CH 3 H 60-62 84 H Cl CH 3 H H CH 3 CH 3 86-87 85 H Br OCH 3 Br H H H 115-116 ____________________________________________________________ ______________
EXAMPLE 2
Dusting Agents
Equal parts of a mixture of active substance and synergistic agent and of precipitated silica are finely ground. Dusting agents, preferably containing 1-6 percent of active substance, can be manufactured therefrom by mixing with kaolin or talc.
Spraying Powder
To manufacture a spraying powder, the following components are for example mixed and finely ground:
50 parts of a mixture of active substance and synergistic agent
20 parts of highly adsorbent silica
25 parts of Bolus alba (Kaolin)
1.5 parts of sodium 1-benzyl-2-stearyl-benzimidazole-6,3'-disulphonate and
3.5 parts of a reaction product of p-tert. octylphenol and ethylene oxide.
Emulsion Concentrate
The easily soluble mixture of active substance and synergistic agent can also be formulated as an emulsion concentrate in accordance with the following instruction:
20 parts of a mixture of active substance and synergistic agent,
70 parts of xylene and
10 parts of a mixture of a reaction product of an alkyl phenol with ethylene oxide and calcium dodecylbenzenesulphonate are mixed. On dilution with water to the desired concentration, a sprayable emulsion results.
Granules
7.5 g of a mixture of active substance and synergistic agent are dissolved in 100 ml of acetone and the acetone solution thus obtained is added to 92 g of granular attapulgite. The whole is well mixed and the solvent is stripped off in a rotary evaporator. Granules containing 7.5 percent of active substance are obtained.
EXAMPLE 3
Test for Synergistic Action
For this test, female house flies aged from 2 to 5 days were used. Before the start of the test, the flies were sorted as to gender under CO 2 narcosis, and the females were placed in groups of 10. The flies, which were kept motionless with CO 2 , were treated with a dispenser which on pressing the button each time releases 1 microlitre of the solution of the test substance in acetone. After the treatment, the flies were placed in groups of 10 in Petri dishes into which a cottonwool pad impregnated with honey water had been introduced for the flies to feed on. After 24 hours the test was evaluated by counting the flies which could no longer move. The results quoted in the table represent average values of the percentage destruction from four repeat tests.
The following were each used per fly (weight of one fly 20 mg (average value)):
a. 0.08γ of each of the compounds Nos. 1, 2, 3, 6, 7, 9, 12, 15, 20, 45, 49, 53, 55, 57 and 78
b. 0.08γ of the compound of formula ##SPC9##
c. 0.08γ of compound (A) and 0.08γ of compounds Nos. 1, 2, 3, 6, 7, 9, 12, 15, 20, 45, 49, 53, 55, 57 and 78.
______________________________________ Compound No. 0.08γ of synergistic agent 0.08γ of (A) 0.08γ of A and 0.08γ of synergistic agent ______________________________________ 1 17 92 2 0 17 65 3 0 17 50 6 0 17 90 7 0 17 40 9 0 17 95 12 0 17 95 15 0 17 45 20 0 17 60 45 0 17 80 49 0 17 65 53 0 17 65 55 0 17 90 57 0 17 45 78 0 17 75 ______________________________________ EXAMPLE 4
A test of the synergistic action of the compound No. 1 on the compounds of formulae ##SPC10##
The results listed in the table represent average values of the percentage destruction of female house flies, from two repeat experiments.
______________________________________ a. 0.32γ Compound No. 1 0 0.32γ (A) 5 0.32γ Compound No. 1 + 0.32γ (A) 84 b. 0.08γ Compound No. 1 0 0.08γ (B) 5 0.08γ Compound No. 1 + 0.08γ (B) 95 c. 0.1γ Compound No. 1 0 0.1γ (C) 3 0.1γ Compound No. 1 + 0.1γ (C) 80 d. 0.2γ Compound No. 1 0 0.2γ (D) 10 0.2γ Compound No. 1+ 0.2γ (D) 99 e. 0.08γ Compound No. 1 0 0.08γ (E) 15 0.08γ Compound No. 1 + 0.08γ (E) 88 f. 0.6γ Compound No. 1 0 0.6γ (F) 15 0.6γ Compound No. 1 + 0.6γ (F) 73 g. 0.1γ Compound No. 1 0 0.1γ (G) 3 0.1γ Compound No. 1 + 0.1γ (G) 78 h. 0.1γ Compound No. 1 0 0.1γ (H) 15 0.1γ Compound No. 1+ 0.1γ (H) 99 i. 0.07γ Compound No. 1 0 0.07γ (I) 10 0.07γ Compound No. 1 + 0.07γ (I) 29 ______________________________________