Classifications

• • 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
  • C07D285/14—Thiadiazoles; Hydrogenated thiadiazoles condensed with carbocyclic rings or ring systems
• • 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
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
  • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D341/00—Heterocyclic compounds containing rings having three or more sulfur atoms as the only ring hetero atoms

Definitions

• This, invention concerns substituted benzopentathiepins, intermediate 1,2.3-benzothiadiazoles and the process: for malcing. the former by reacting the latter with elemental sulfur.
• Uhsubstituted benzopentathiepin is known (Feher et al., Z. Anorcr. Alia. Chem.. 452,. 37 to 42 (1979): Feher et al., Tet. Lett., 2125, to 2126 (1971). It, is prepared from 1,2-benzenedithiol and S 3 Cl 2 . No utility is described, Feher et al., in Z. Naturforsch. B, 27, 1006. (1972). describe preparation of the 7,8-dimethyl derivative by a similar method. A reduced hexahydr ⁇ benzopentathiepin was prepared by Feher et al., according to the method of Feher et al. described above: Angew. Chem. Int.
• Watkins et al., J. Her. Chem.. 19. 459 to 462 (1982) describe the x-ray crystal structure of a complex indene pentathiepin. Synthesis and utility are not described.
• R H, C 1 -C 6 alkyl, C 5 -C 6 cycloalkyl.
• the 1,2-benzenedithiols can. be prepared by pyrolysis of benzothiadiazoles in the presence of carbon disulfide and alkaline hydrolysis of the intermediate trithiocarbonate: Hunig et al., Liebigs Ann. Chem. , 738, 192 to 194 (1970). The process requires a pressure vessel and temperatures of 220°C.
• R 1 , R 2 and R 3 are the same or different substituents that do not react with sulfur at elevated temperatures and are selected from H (no more than two of R 1 , R 2 and R 3 being H), X,
• R 4 is selected from aryl. substituted aryl and substituted and unsubstituted branched or straight chain C 1 to C 6 alkyl;
• X is selected from Cl, Br and F.
• R 1 , R 2 and R 3 substituents are selected from X, CX 3 , OR, SR,
• benzopentathiepins of this invention are those wherein: (1)
• R 1 and R 3 are both H and R 2 is selected from X,
• R 1 is selected from X, CX 3 , SR 4 , OR 4 , NR 4 2 , COOR 4 , aryl and substituted aryl; and (3) R 1 and, R 2 are both NR 4 2 and R 3 is H.
• Especially preferred compounds are those in category (1) wherein R 2 is N(CH 3 ) 2 , OCH 3 , CF 3 or Cl; those in category (2) wherein R 1 is CF 3 or Br; and the compound in category (3) wherein R 4 is methyl.
• the latter compound is named
• This invention also concerns the method for making benzopentathiepins by the following reaction:
• the reaction is typically carried out in an inert solvent at temperatures between about 140o to 200°C, with about 160o to 190oC being preferred.
• Suitable solvents are those which are inert to elemental sulfur and are tolerant of temperature and pressure combinations required to meet the temperature, range described.
• the solvents include but are not limited to decahydronaphthalene, nitrobenzene, dichlorobenzenes. dimethylformamide and dimethyl sulfoxide.
• the reaction is normally carried out in an inert atmosphere such as nitrogen, argon, helium and the like.
• the molar ratio of elemental sulfur (calculated as S 8 ) to benzothiadiazole can range from about 1:2 to 2:1; the preferred ratio is about 1:1.
• This invention also concerns the method for making said benzopentathiepins in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO):
• the molar ratio of DABCO to benzothiadiazole is about 0.1:1 to 2:1; the preferred ratio is about 1:1.
• Employing DABCO in the process of the invention has been found to increase product yields substantially. This invention also concerns these novel benzothiadiazoles:
• This invention also concerns the method for making substituted 1,2-benzenedithiols by reduction of benzopentathiepins according to the reaction:
• Suitable reducing agents for said process include but are not limited to sodium borohydride. lithium aluminum hydride, trialkyl phosphites, zinc/ aqueous acid, and the like. Sodium borohydride and lithim aluminum hydride are preferred.
• the reaction temperature can be about 0o to 60oC; the preferred range for sodium borohydride, for reasons of ease of reactivity, is about 20o to 40o C; the preferred range for lithium aluminum hydride is about 0o to 35oC.
• the molar ratio of sodium borohydride or lithium aluminum hydride to benzopentathiepia can range from about 2:1 to 6:1; a ratio of about 4:1 is preferred.
• the process employing lithium aluminum hydride should be run in the absence of water.
• the reaction process initially gives a dithiolate salt which caa be further reacted with aqueous acid to give the 1,2-benzenedithiols ⁇ or with alkylating agents such as methyl iodide to give di-thioethers.
• alkylating agents such as methyl iodide
• An additional aspect of this invention concerns the use of selected benzopentathiepins as anti-fungal and anti-viral agents.
• the compounds of Table 1 were found to be effective against the recited fungus and virus types. Details concerning formulations and control methodology follow the Table.
• CPM cucumber powdery mildew
• BPM barley powdery mildew
• CMV cucumber mosaic virus
• WLR wheat leaf rust
• benzopentathiepins caa be prepared in conventional ways. They include dusts, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of them caa be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions can be used primarily as concentrates which are to be diluted prior to ultimate use.
• the formulations broadly, contain about 1% to 99% by weight of active ingredient(s) and at least one of (a) about 0.1% to
• surfactaat(s) and (b) about 1% to 99% solid or liquid diluent(s). More specifically, they will contain these ingredients in the approximate proportions set forth in Table 2 with the active ingredient plus at least one surfactant or diluent being equal to 100 weight percent.
• Agricultural formulations that contain the compounds of this invention as active ingredient can also contain other active ingredients.
• the additional agricultural chemicals are employed in mixtures or combinations in amounts ranging from 0.05 to 25 parts by weight for each part by weight of the compound or compounds of this invention. The proper choice of amounts is readily made by one skilled in the art of protecting plants from pests.
• Fungicides methyl 2-benzimidazolecarbamate (carbendazim) tetramethylthiuram disulfide (thiuram) n-dodecylguanidine acetate (dodine) manganese ethylenebisdithiocarbamate (maneb) 1,4-dichloro-2.5-dimethoxybenzene (chloroneb) methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate
• Fine solid compositions are made by blending and. usually, grinding as in a hammer or fluid energy mill.
• Suspensions are prepared by wet milling.
• Granules and pellets can be made by spraying the active material on preformed granular carriers or by agglomeration techniques.
• Disease control is accomplished by applying the compounds of this invention to the portion of the plant to be protected.
• the compounds can be applied as preventive treatments prior to inoculation with the pathogen, or after inoculation as a curative post-infection treatment. Rates of application for compounds of this invention will be influenced by specific host plants, fungal pathogens, and many factors of the environment must be determined under use conditions. Foliage sprayed with concentrations ranging from 1 to 500 ppm of active ingredient can be protected from disease under suitable conditions.
• the benzopentathiepins of this invention have generic utility as intermediates in the preparation of substituted 1,2-benzenedithiols which are free of the 1,3-and 1,4-dithiol isomers.
• substituted 1,2-benzenedithiols are known intermediates to pharmaceuticals (U.S. 4,242,510; Sindelar et al., Collect. Czech. Chem. Comm., 47, 72 to 87 (1982), pesticides (U.S. 3,746,707). and rubber crosslinking agents (U.S. 3,979,369).
• Examples 1 to 7 and 16 illustrate the process of the invention for preparation of benzopentathiepins.
• Examples 2 to 7 and 16 illustrate novel benzopentathiepins.
• Examples 8 to 10 illustrate the yield enhancement of the process by employing DABCO.
• Examples 11, 12 and 15 illustrate the novel benzothiadiazole compounds.
• Examples 13 and 14 illustrate the process for conversion of benzopentathiepins to dithiols. In both Examples 13 and 14, the dithiols obtained are isolated as bismethylthioethers to prevent aerobic oxidation. These bismethylthioethers can be converted back to the benzenedithiols by treatment with, for example, sodium in liquid ammonia.
• Decalin® (20 mL) was heated to 175°C for 1.25 h and nitrogen was evolved. The mixture was cooled and the solvent was removed by Kugelrohr distillation. The residue was preadsorbed and chromatographed (300 g) on Silica Woelm® TSC (1%. ether-hexane) to give first sulfur and then 2.2 g of a sulfur-product mixture.
• the above salt was slurried in 5% aqueous HCl (100 mL) and chilled to 0°C.
• a solution of sodium nitrite (3.22 g) in water (15 mL) was added dropwise over 20 min to the stirred mixture; then it was neutralized to pH 9 with 20% aqueous sodium hydroxide.
• the reaction was extracted with ether (3 x100 mL) and the organic phase was washed with water and brine and then filtered through a cone of sodium sulfate.
• This Example illustrates the making of a compound useful (as the unprotected dithiol) as a rubber cross-linking agent.
• This Example illustrates the making of a compound useful as an intermediate (as the unprotected dithiol) to a tricyclic psychotropic agent.
• 7-chlorobenzopentathiepin (0.32 g, 1.18 mmol) was dissolved in tetrahydrofuran (30 mL) and ethanol (30 mL) was added.
• Sodium borohydride (0.22 g, 5.91 mmol) was added over 5 min in portions at ambient temperature causing the solution to evolve hydrogen gas and warm slightly. After gas evolution had ceased in about 15 min, water (10 mL) was added and the mixture was heated to about 50°C for 5 min and cooled to ambient temperature.
• Methyl iodide (0.44 mL, 7.0 mmol) was added and the solution was stirred. The solvents were removed and the residue was partitioned between ether and water. The phases were separated and the organic layer was washed with brine and dried through a cone of sodium sulfate.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Agronomy & Crop Science (AREA)
• Pest Control & Pesticides (AREA)
• Plant Pathology (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Dentistry (AREA)
• General Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
• Environmental Sciences (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)

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• 1984
  • 1984-06-07 EP EP19840902416 patent/EP0146610A4/de not_active Withdrawn
  • 1984-06-07 WO PCT/US1984/000870 patent/WO1984004921A1/en not_active Application Discontinuation
  • 1984-06-07 HU HU299184A patent/HUT35926A/hu unknown
  • 1984-06-07 AU AU30160/84A patent/AU3016084A/en not_active Abandoned
  • 1984-06-07 JP JP50232884A patent/JPS60501503A/ja active Pending
  • 1984-11-28 FI FI844675A patent/FI844675L/fi not_active Application Discontinuation
• 1985
  • 1985-02-07 DK DK56985A patent/DK56985D0/da not_active Application Discontinuation

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