US3090721A - Thiadiazole - Google Patents

Thiadiazole Download PDF

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Publication number
US3090721A
US3090721A US792953A US79295359A US3090721A US 3090721 A US3090721 A US 3090721A US 792953 A US792953 A US 792953A US 79295359 A US79295359 A US 79295359A US 3090721 A US3090721 A US 3090721A
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Prior art keywords
thiadiazole
nematodes
chloro
composition
weight
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Expired - Lifetime
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US792953A
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English (en)
Inventor
Uhlenbroek Jan Hendrik
Bijloo Johan Dirk
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US Philips Corp
North American Philips Co Inc
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US Philips Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/08—1,2,4-Thiadiazoles; Hydrogenated 1,2,4-thiadiazoles

Definitions

  • 1.2.4-thiadiazoles in which a. halogen atom is linked to one of the carbon atoms of the ring are active against noxious organisms and in particular have a nematocide effect.
  • the present invention relates to a method of producing a means for combating noxious organisms and in particular nematodes, characterized in that a compound of the general formula:
  • Hlg represents a halogen atom and R represents a phenyl group or a group R .
  • S- in which R represents a whether or not substituted, saturated or unsaturated, alkyl-, cycloalkyl-, arylor aralkyl group, the aliphatic chain whether or not being interrupted by oxygen or sulphur, is mixed with inert, solid or fluid carriers, if desired with the addition of surface-active materials and/ or dispersion agents.
  • a satisfactory nematocide effect have, in particular, the compounds according .to the invention, in which I-Ilg represents a chlorine atom and R represents an alkyl group with 1 to 12 carbon atoms such as methyl-, ethyl-, propyl-, isopropyl-, butyl-, isobutyl-, isoamyl-, hexylor octyl group or an oxygen interrupted alkyl group such as an ethoxyethyl group or an unsaturated group, for example an allyl group and further compounds, in which R represents a phenyl-, 4-chlorophenyl-, 4-methylphenyl group or a benzylor 4-chlorobenzyl group or a phenoxyethyl group.
  • Excellent nematocides are compounds according to the invention in which Hlg is a chlorine atom and R represents a phenyl group, as well as those in which R represents an unbranched alkyl. group comprising 1 to 6 carbon atoms, an allyl group, an ethoxyethyl group or a phenyl-, 4-chlorophenyl or 4-methylphenyl group or a benzylor 4-chlorobenzyl group.
  • nematodes are attacked by compounds according to the invention which cause eel worm diseases in plants, for example Heterodera species, for example larvae of Heterodera rostochz'ensis (potato cysticolous eel worm), Meloidogyne species (root knob eel worms) Ditylenchus species (stem eel worms), Pratylenchus species, Hoplolaimus species and larvae of Anguina triiicz (wheat gall eel worms).
  • Heterodera species for example larvae of Heterodera rostochz'ensis (potato cysticolous eel worm), Meloidogyne species (root knob eel worms) Ditylenchus species (stem eel worms), Pratylenchus species, Hoplolaimus species and larvae of Anguina triiicz (wheat gall eel worms).
  • Tests showing the nematocide etfect of compounds according to the invention were carried out as follows.
  • the tests were carried out on larvae of Heterodera rostochiensis lured for two days from their cysts, Ditylenchus dipsaci and larvae of Anguina tritici (both specimens soaked for 17 hours from 'dry condition).
  • Table I states the minimum lethal dosage of the investigated compound, killing all the test specimens within 140 hours exposure.
  • the minimum lethal dosage stated is the concentration of the active compound of the suspension used, expressed in parts by weight of active compound per million parts by weight of diluent (water).
  • Nematode Heterodera rostuchiensz's 100 100 100 100 100 100 100 100 Ditylenchus dipsaci 100 100 30 Anguinctritici (larvae) 100 100 100 100 100 60 and subsequently stored for 24 days in cups at approximately 15 C. In order to prevent drying out of the soil the cups were covered with a polythene foil. The nematodes were subsequentl-ywashed out of the soil in the manner referred to by 'I. W. Seinhorst and the survivors were counted (see Nematologica, vol. 1, pages 249 to 267 (1956)). The same was done with blank-tests without adding active substance to the soil.
  • Table III states the average result of these tests for each of the following compounds:
  • UE 9:3-phenyl-5-chloro-1.2.4-thiadiazole, I UE 18 B-methylmercapto-S-chloro-1.2.4-thiadiazole, UE 19':3-n.butylmercapto-5-chloro-1.2.4-thiadiazole, UE 32:3-n.propylrnercapto-5-chloro-1.2.4-thiadiazole.
  • the active compounds according to the invention may be mixed with a pulverulent inert carrier, for'exa-mple chalk, dolomite, attapulgite, kaolin or pipe clay, or dissolved or dispersed in an inert solvent such as toluene, xylene, aliphatic or aromatic ketones, for example acetone, methyl-ethylketone or cyclohexanone, or mixtures of them with said hydrocarbons, if desired with the addition of surface-active materials and/or dispersion agentsj
  • these preparations may be mixed with synthetic tertilisers.
  • a dust is prepared by grinding approximately 5 parts by weight of an active compound according to the invention together with approximately 95 parts by weight of kieselguhr to an average particle size of approximately ;r.
  • a wettable powder is produced by mixing approximately 50 parts by weight of an active compound according to the invention with approximately 5 parts by weight of oleylamido-methyltaurate, approximately 10 parts by weight of calciumligninsulfonate and approximately 35 parts by weight of dolomite (calcium-magnesium carbonate), this mixture being ground to an average particle size of approximately 10;!
  • Miscible oils may, for example, be produced by dissolving approximately 25 parts by weight of an active compound according to the invention in a mixture of approximately 10 parts by weight of an active compound according to the invention in a mixture of approximately 10 parts by weight of polyoxyethylenesorbitan fatty acid ester, approximately 10 parts by weight of methylethylketone and approximately 55 parts by weight of xylene.
  • the compounds according to the invention permit in general,.miscible oils of :high concentration to be produced.
  • 3-n.butylmercapto-S-chloro- 1.2.4-thiadiazole with xylene can be worked up to a miscible oil containing 80 percent by weight of active material. This may be of importance in practice.
  • R represents the group R 8
  • R 8 has, however, not yet been mentioned in the literature.
  • These compounds can be produced by the aforesaid method from isothiouronium salts and perchloromethylmercaptan.
  • Novel compounds are inter alia those in which in the aforesaid formula R represents one of the following groups: isopropyl, l-methylpropyl, 3-methylpropyl, namyl, n.hexyl, noctyl, n.dodecyl, allyl, ethoxyethyl, phenyl, '4-chl0rophenyl, 4-methylphenyl and phenoxyethyl.
  • Example I II-PHENYLMERCAPTQ-5(THLORO-l.2A FHIADIAZOLE NE I l l O-Cl In a 3 litre flask, 188.5 gms. (1.0 mole) of phenylisothiouroniumchloride were mixed with 186 gms. (1.0 mole) of perchloromethylmercaptan, 180 ccs. of water and 300 ccs. of methylenechloride, while cooling the flask with ice-water. Subsequently, a solution of 160Jgms. (4.0 mole) of sodium-hydroxide in 500 ccs. of water was slowly added to the mixture, while'stirring vigorously.
  • Example II 3-n.OCTYLMERCAPTO-fi-CHLORO-l.2A-THIADLAZOLE' 22.4 gms. (yield 68%) of 3-n.octyl-mercapto-S-chloro- 1.2.4-thiadiazole were obtained from 33.6 gms. (0.125 mole) of n.-octylisothiouronium bromide and 23.3 gms. (0.125 mole) of perchloromethylmercaptan. Boiling point: 145 to 146 C. at 8 mms. mercury pressure.
  • Example III 3-ALLYLMERCAPTO-5-CHLORO-1.ZA-THIADIAZOLE 22.2 gms. (yield 46%) of 3-allylmercapto-5-chloro- 1.2.4-thiadiazole were produced from 49.3 gms. (0.25 mole) of allylisothiouronium bromide and 46.5 gms. (0.25 mole) of perchloromethylmercaptan. Boiling point 117 C. at 15 mms. mercury pressure,
  • the compounds according to the invention can be produced from the corresponding 5-amino-l.2.4-thiadiazoles according to the reaction of Sandmeyer, in which the amino compounds are converted into diazonium compounds by means of nitrite, for example sodium nitrite, which diazoniurn compounds are converted into S-chloro-1.2.4-thiadiazoles in the presence of copper powder and a chloride, or in the presence of, for example, cuprous chloride.
  • Example VI 3-BENZYLMERCAPTO-5CHLORO-1.2.4-THIADIAZOLE 9.5 gms. (0.043 mole) of 3-benzyhnercapto-5-amino- 1.2.4-thiadiazole were dissolved in 100 ccs. of acetic acid. Whilst cooling with ice a solution of 4.9 gms. (0.07 mole) of sodium nitrite in 50 ccs. of concentrated hydrochloric acid was added dropwise such that the temperature of the mixture did not exceed 20 C. After standing 15 mintries at room temperature, the reaction mixture was poured out while stirring, in a solution of 6 gms. of cuprous chloride in 100 ccs. of concentrated hydrochloric acid.
  • the 3-phenyl-5chloro-1.2.4-thiadiazole was extracted with petroleum ether (boiling range 40 C. to 60 C.) from the reaction mixture. Yield 6.85 gms. (58%). Melting point 42 C. to 50 C.
  • composition for the control of nematode comprising as an active ingredient a thiadiazole compound corresponding to the general formula:
  • Hal represents a halogen atom and R represents a radical selected from the group consisting of phenyl and the radical R 8 wherein R represents a radical se- 'lected from the group consisting of alkyl, alkoxyalkyl, allyl, phenyl, methylphenyl, chlorophenyl, benzyl, chlorobenzyl and phenoxyethyl in a nematocidal effective amount, a surface active material and a nematocide adjuvant as a carrier therefor.
  • a dust for combating nematodes comprising an intimate mixture of about 5 parts by weight of the active compound of claim 1 and about parts by weight of kieselguhr, said dust having an average particle size of approximately 10;!
  • a wettable powder for combating nematodes comprising an intimate mixture of about 50 parts by weight of the active compound of claim 1, about 5 parts by weight of oleylamidomethyllaurate, about 10 parts by Weight of calcium ligninsulfonate and about 35 parts by weight of dolomite, said powder having an average particle size of about 10a.
  • a miscible oil for combating nematodes comprising a solution of about 25 parts by weight of the active compound of claim 1 in a mixture of about 55 parts by weight of xylene, of about 10 parts by weight of methylethyl-ketone and of about 10 parts by weight of polyoxyethylene-sorbitan fatty acid ester.
  • a composition for the control of nematodes comprising as an active ingredient 3-phenyl-5-chloro-l,2,4- thiadiazole in a nematocidal effective amount, a surface active material and a nematocide adjuvant therefor.
  • a composition for the control of nematodes comprising as an active ingredient 3-alkylmercapto-5-chloro- 1,2,4-thiadiazole in a nematocidal effective amount, a surface active material and a nematocide adjuvant therefor.
  • a composition for the control of nematodes comprising as an active ingredient 3-ethoxyethylrnercapto-5- chloro-l,2,4-thiadiazole in a nematocidal effective amount, a surface active material and a nematocide adjuvant therefor.
  • a composition for the control of nematodes comprising as an active ingredient 3-phenylmercapto-5-chloro- 1,2,4-thiadiazole in a nematocidal effective amount, a surface active material and a nematocide adjuvant therefor.
  • a composition for the control of nematodes comprising as an active ingredient 3-n-butylmercapto-5-chloro-l,2,4-thiadiazole in a nematocidal effective amount, a surface active material and a nematocide adjuvant therefor.
  • a composition for the control of nematodes comprising as an active ingredient 3-methylmercapto-5-chlor-.1,2,4-thiadiazole in a nematocidal efiective amount, a surface active material and a nematocide adjuvant therefor.
  • a composition for the control of nematodes comprising as an active ingredient 3-(4 -ch1orophenyl)-mercapto-S-chloro-1,2,4-thiadiazole in a nematocidal effective amount, a surface active material and a nematocide adjuvant therefor.
  • a composition for the control of nematodes comprising as an active ingredient 3-(4 -methylpheny-D-mercapto-S-chloro-l,2,4-thiadiazole in a nematocidal effective amount, a surface active material and a nematocide adjuvant therefor.
  • a composition for the control of nematodes comprising as an active ingredient S-benzylmercapto-5-chloro- 1,2,4-thiadiazole in a nematocidal effective amount, a surface active material and a nematocide adjuvant there for.
  • Acomposi-tion for the control of nematodes comprising-as an active ingredient 3-(4 -henzylmercapto)-5- chloro-1,2,4thiadiazole in a nematocidal effective amount, a surface active material and a nematocide adjuvant therefor.
  • a method of combating nematodes comprising treating the habitat thereof with the composition of claim 1.
  • a method of combating nematodes comprising treating the habitat thereof with the composition of claim 11.
  • a method of combating nematodes comprising treating the habitat thereof with the composition of claim 13.
  • a method of combating nematodes comprising treating the habitat thereof With; the composition of claim 14.
  • a method of combating nematodes comprising treating the habitat thereof with the composition of claim 15.
  • a method of combating nematodes comprising treating the habitat thereof with the composition of claim 16.
  • a method of combating nematodes comprising treating the habitat thereof with the composition of claim 17.
  • a method of combating nematodes comprising treating the habitat thereof with the composition of claim 18.

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US792953A 1958-02-13 1959-02-13 Thiadiazole Expired - Lifetime US3090721A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3159644A (en) * 1960-04-11 1964-12-01 Monsanto Co 3-halo(or nitro)-phenylalkylmercapto-5-halo(or nitro)-1, 2, 4-thiadiazole
US3169969A (en) * 1962-05-15 1965-02-16 Rhone Poulenc Sa 3-trichloromethylthio-5-halo-1, 3, 4-thiadiazol-2-one
US3192103A (en) * 1962-04-17 1965-06-29 Union Carbide Corp Method of combating nematodes
US3260588A (en) * 1961-03-15 1966-07-12 Olin Mathieson Method for controlling pests
US3370064A (en) * 1960-11-02 1968-02-20 Ici Ltd Certain 4-(chlorophenylhydrazono)-2-isoxazolin-5-ones
US3419572A (en) * 1964-09-30 1968-12-31 Merck & Co Inc Ring synthesis of halo-substituted 1,2,5-thiadiazoles
US3903099A (en) * 1970-09-04 1975-09-02 Ciba Geigy Corp Certain 2-halo-5-thio-1,3,4-thiadiazoles
US4081453A (en) * 1971-11-12 1978-03-28 The O. M. Scott & Sons Company Certain 3,5-dihalo-1,2,4-thiadiazole preparations

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2285410A (en) * 1941-02-27 1942-06-09 Du Pont Pest control
US2592195A (en) * 1939-12-20 1952-04-08 Gevaert Photo Prod Nv Heterocyclic nitrogen compounds
US2702803A (en) * 1954-04-12 1955-02-22 Lilly Co Eli Substituted heterodiazoles
US2744908A (en) * 1954-01-27 1956-05-08 American Cyanamid Co Process for preparing substitutedmercapto-1, 3, 4-thiadiazoles
US2863804A (en) * 1956-09-11 1958-12-09 Alex M Fuqua Method of treating mange with extract of cedar leaf

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2592195A (en) * 1939-12-20 1952-04-08 Gevaert Photo Prod Nv Heterocyclic nitrogen compounds
US2285410A (en) * 1941-02-27 1942-06-09 Du Pont Pest control
US2744908A (en) * 1954-01-27 1956-05-08 American Cyanamid Co Process for preparing substitutedmercapto-1, 3, 4-thiadiazoles
US2702803A (en) * 1954-04-12 1955-02-22 Lilly Co Eli Substituted heterodiazoles
US2863804A (en) * 1956-09-11 1958-12-09 Alex M Fuqua Method of treating mange with extract of cedar leaf

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3159644A (en) * 1960-04-11 1964-12-01 Monsanto Co 3-halo(or nitro)-phenylalkylmercapto-5-halo(or nitro)-1, 2, 4-thiadiazole
US3370064A (en) * 1960-11-02 1968-02-20 Ici Ltd Certain 4-(chlorophenylhydrazono)-2-isoxazolin-5-ones
US3260588A (en) * 1961-03-15 1966-07-12 Olin Mathieson Method for controlling pests
US3192103A (en) * 1962-04-17 1965-06-29 Union Carbide Corp Method of combating nematodes
US3169969A (en) * 1962-05-15 1965-02-16 Rhone Poulenc Sa 3-trichloromethylthio-5-halo-1, 3, 4-thiadiazol-2-one
US3419572A (en) * 1964-09-30 1968-12-31 Merck & Co Inc Ring synthesis of halo-substituted 1,2,5-thiadiazoles
US3903099A (en) * 1970-09-04 1975-09-02 Ciba Geigy Corp Certain 2-halo-5-thio-1,3,4-thiadiazoles
US4081453A (en) * 1971-11-12 1978-03-28 The O. M. Scott & Sons Company Certain 3,5-dihalo-1,2,4-thiadiazole preparations

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