• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to new nitrothiophenes of the general formula therein R is an alkyl group having 1-12 carbon atoms, which alkyl group may be substituted with a phenyl group substituted, if desired, with nitro, halogen, alkyl with 1-4 carbon atoms or alkoxy with 1-4 carbon atoms, with an alkoxycarbonyl group having 2-5 carbon atoms, orwith a thiocyanato group, or R is a phenyl group, a pyridyl group or a N-oxypyridyl group, which groups may be substituted with nitro, halogen, alkyl with 1-4 carbon atoms, or alkoxywith 1-4 carbon atoms; R1 is a hydrogen atom, a halogen atom, an alkyl group having 1-4 carbon atoms, or a phenyl group substituted or not substituted with nitro, halogen, alkyl with 1-4 carbon atoms, or alkoxy with 1-4 carbon atoms; R2 is a hydrogen atom, an alkyl group having 1-4 carbon atoms, a cyano group, an alkanoyl group having 1-5 carbon atoms, an a,a-dialkoxyalkyl- or a,a- alkylenedioxyalkyl group having 3-10 carbon atoms, a carboxy group, an alkoxycarbonyl group having 2-5 carbon atoms, an a-hydroxyalkyl group having 1-4 carbon atoms, an a-haloalkyl group having 1-4 carbon atoms, an a-alkoxyalkyl group having 2-6 carbon atoms, an alkoxycarboximidoyl group having 2-5 carbon atoms, a sulpho group, an amino-, alkylamino- or dialkylaminosulphonyl group, the alkyl group(s) of which has (have ) 1-4 carbon atoms, or an alkoxysulphonyl group having 1-4 carbon atoms, and n is 0-2. The compositions are particularly suitable to prevent infections by phytophagous microorganisms in agriculture and horticulture. For this purpose the seed is treated priorto sowing or the soil destined for sowing or planting is treated with the composition in a dosage from 100 to 1,500 mg of active substance per kg of seed and from 2 to 100 kg of active substance per hectare, respectively.
    公开号:SU1050564A3
    申请号:SU813276203
    申请日:1981-05-04
    公开日:1983-10-23
    发明作者:Долман Хендрик；Кэйперс Йоханнес
    申请人:Дюфар Интернэшнл Рисерч Б.В. (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to a process for the preparation of new nitrothiophene derivatives of the general formula R IOrgN SS (0) aK where R is alkyl with 1-7 carbon atoms, which can be substituted by an alkoxycarbonyl group with 2-5 carbon atoms or a thiocyanate group, or phenyl, pyridyl or N-pyridyl, which may be replaced by a nitro group, a halogen or C, an alkoxy group; R is hydrogen, halogen, C-C alkyl and phenyl; P2 is hydrogen, C alknyl, cyaC-alkanoyl, S ; p "1 or 2, which have a fungicidal and / or bactericidal effect and can therefore be used in agriculture. The patent and technical department has extensively described the production of salts of foxides and sulfones by the oxidation of suficides, for example, hydrogen peroxide or peracids. The reaction is carried out in an environment of polar organic solvents temperature from to the boiling point of the solvent depending on the type of reagents and solvents used C1 3. The purpose of the invention is to develop a method for producing new nitrothiophene derivatives that would have valuable properties. The goal is achieved that according to the method for producing nitrothiophene derivatives of the formula T, Formulas Ij RI HO-0 have the above mentioned and are oxidized. Oxidation is carried out with peroxycarboxylic acid or hydrogen peroxide, meaning 42 In the preparation of sulfones, the oxidizing agent is hydrogen peroxide. Oh yeah. When peroxycarboxylic acids, such as p-nitroperbenzoic acid or m-chloroperbenzoic acid, are used, the sulfide is oxidized selectively to the sulfoxide. These reactions can be carried out in polar solvents such as acetic acid, alcohols such as methanol, or chlorinated hydrocarbons, such as chloroform. The reaction temperature depends on the type of reagent and solvent used and can vary from 0 ° C to the boiling point of the solvent. After the desired product has been isolated, it can be purified, if necessary, by recrystallization. Example 1. Preparation of 2-methylsulfinyl-3-nitrothiophene. 0.95 g of p-nitroperbenzoic acid is added to a solution of 0.88 g of 2-methylthio-3-nitrothiophene in 15 ml of chloroform at 0-10 ° C. After stirring for 2 hours at 5 ° C, a solution of 2 g of sodium bicarbonate is added approximately in 50 ml of water; then the reaction mixture is moved within 15 minutes. The chloroform layer is separated, rinsed with water and filtered. After distilling off the solvent, get the target product in the amount of 100%, so pl. . ve 0.95 g, yield The following compounds are prepared in a similar manner, where, if necessary, m-chloroperbenzoic acid is used as an oxidizing agent and methanol as a solvent: 2-methylsulfinyl-3-nitro-4-methylthiophene, m.p. 142С; 2-methylsulfinyl-3-nitro-5-ethoxycarboxyimidoylthiophene, mp 210 C; 2-methylsulfinyl-3-nitro-5-cyanothiophene, so pl. 2-methylsulfinyl-3-nitro-4,5-dimethylthiophene, so pl. 156 ° C; 2- (4-chlorophenylsulfonyl CZ-nitrothiophene, mp 163-165 ° C; 2-phenylsulfinyl-3-nitrothiophene, mp 124-126 0; 2- (4-methoxyphenylsulfinyl / -3-nitrothiophene, t mp 156-157 with; 2-methylsulfinyl-3-nitro-5-ethoxycarbonylthiophene, mp 95-99 ° C; 2-methylsulfinyl-3-nitrothiophene 5 mp, 79-82 ° C; 2- n-propylsulfinyl-3-nitrothiophene, mp: 8i-84 ° C; 2-isobutylsulfinyl-3-nitrothiophene, mp: 9 -93 ° C; 2-methylulphinyl-3-nitro-5-acetylthiophene, t 2- 3-nitrothienyl- (2) -sulfinyl pyridine-N-oxide, mp; (decomp.); 2- (4-nitrophenylsulfinyl) t3-nitrothiophene, mp 194-196 0; 2 -methylsulfinyl-3-nitro-4-phenylthiophene, mp. 171-. 2-n-gene Tylsulfinyl-3-nitrothiophene, mp 68-7l C; 2-ethoxycarbonylmethylsulphinyl-3-nit rothiophene, t.th. , mp. (decomp.); 2-phenylsulfinyl-3-nitro-5-cyanothiophene, mp 158-160 ° C; 2-3g nitrothienyl (2): sulfinyl-3 nitropyridine, mp 181-183c (dec. 2-methylsulfinyl-3-nitro-4-chlorothiophene, mp. 114-116 0; 2-thiocyanatomethylsulfinyl-3-nitrotyo phen; m.p. 138-14,0С; 2-methylsulfinyl-3-nitro-5-H, N-dimethylaminosulfonylthiophene, mp | 53154 0; 2-ethylsulfinl-3-nitro-5-acetylthiophene, so pl. (with decomposition); 2-methylsulfinyl-3-nitro-5-hydroxymethyl thiophene, m.p. P2.5-113,. 2-methylsulfinyl-3-nitro-5-and-hydroxy ethyl) -thiophene, so pl. 118.5-120.5 ° C; 2-methylsulfnyl-3-nitro-5-ethylene dihydroxymethylthiophene, m.p. 125-126, 2-methylsulfinyl-3-nitro-5-bromo-thiophene, m.p. 138-139 C. Example 2. Preparation of 3-methylsulfonyl-3-nitrothiophene. 1., 25 MP of a solution of hydrogen peroxide in water is poured to the office of a thief 0.88 g of 2-methylthio-3-nitrothiophen in 10 units of acetic acid at a temperature of approximately. After heating at about a temperature of approximately: 30 minutes, another 25 ml of the same hydrogen peroxide solution is added. After heating at about 100 ° C for 3 hours, the reaction mixture is cooled and poured into water. The precipitated 2-methylsulfonyl-3-nitrothiophene is left and dried, and the weight of the product is 0.85 g; yield 82%, T.Sh1. . In a similar manner, the following compounds are obtained: 44 2-methylsulfonyl-3-nitro-4-methylthiophene, m.p. 2-methylsulfonyl-3-nitro-4-phenylthiophene, so pl. 119-120 ° C; 2-ethylsulfonyl-3-nitrothiophene, so pl. 84-86 ° C; 2-n-propylsulfonyl-3-nitrothiophene, mp: 49-52 ° C; 2-methylsulfonyl-3-nitro-5-cyiotiophene, so pl. 175-177 ° C; 2-ethoxycarbonylmethylsulfonyl-3-nitrothiophene, m.p. 96-98 s; 2-phenylsulfonyl-3-nitro-5-zenothiophene, so pl. 178-180 ° C; 2-methylsulfonyl-3-nitro-5-adylthiophene, t.cl. 160-161 ° C; 2-thioethylaminomethylsulfonyl-3-nitrothiophene, m.p. 144-147 C; 2-methylsulfonyl-3-Sh1tro-5-H, M-dnmethylaminosulfonylthiophene, m.p..175- / 2-ethylsulfonu-1-3-nitro-5-a1hethylthiophene, m.p. 137.5-138, 2-methylsulfonyl-3-nitro-5-hydroxnmeti l thiophene, m.p. 101-, 5-Yu 2.50; 2-metstsulfonyl-3-nitro-5- (1-hydroxyethyl) -thiophene so pl. 91-92 0; 2-methylsulfonyl-3-nitro-5-ethylenedioxnmethylthiophene, t.p1; 142-143 °. PRI me R 3. Obtaining 2-thiocyanomethylthio-3-nitrothiophene. A solution of 12.8 ml of monochloro acetalg degive in 12.8 ml of water is added to a solution of 35.0 g of 2-nitroethylene-1-, ITAH thiol potassium in 225 ml of water at. stirring at room temperature. The reaction mixture was cooled; the reaction was stopped until, after which 1 ml of concentrated hydrochloric acid and 16 ml of a concentrated solution of potassium ri-sodium hydroxide were added successively, both reagents were added over 5 minutes. After their introduction, the reaction mixture is stirred for 5 minutes. Thereafter, 13 ml of chloromethyl thiocyanate was introduced over 5 minutes. The reaction mixture was stirred at room temperature for 1.5 hours and left overnight. Dichloromethane is added and the reaction mixture is stirred at room temperature for 0.5 hours. After the precipitate is filtered off on a vacuum funnel, the dichloromethane layer is separated and washed with water. The solvent is evaporated and the product is purified on a chromatographic column. As a result, the desired product is obtained, yield 7.1 gm. Mp. 86-87 0. In a similar way, the following compounds are obtained: 2-ethylthio-3-nitrothiophene, m.p. 5153 С; 2-ethylthio-3-nitro-4-methylthiothiophene, mp, 104 ° C. - An example. Preparation of 2-methyl thio-3-nitro-5-cyanothiofeck. A solution of sodium methyl mercaptide is prepared by adding 5 ml of methyl mercaptan to 1.75 g of sodium in 60 ml of abalic ethanol. While stirring and cooling this solution to a temperature below its inflow, a | from to a solution of 17.6 g of 2 bromo-3-nitro-5-formylthiophene and 200 ml of ethanol. 200 ml of water are added to stirring at room temperature for another 2 h, after which the precipitated precipitate is suctioned on a vacuum funnel and the water is washed with water: eHon lJl (by volume} and recrystallized from isopropanol. Thus, 6 are obtained. 5 g of 2-methylt-3-nitro-5-fory-Shtiofen, m.p. 12913 C. To 2.50 g of formic acid are sequentially added 2.35 g of NaHCO 3.1 g of 2-methylthio-3-nitro-5-formylthiophene and 1.2 g of NH, a SUCTION. The reaction mixture is boiled for 1 h, npc is then added to the ode and the precipitate is filtered off on a vacuum funnel. After recrystallization from isopropanol, the target product 2-methylthio-3-nitro-5, -cyanothiophene is obtained, yield 2.3 g, mp 150 New compounds exhibit a fungicidal and / or bactericidal action. They are much more effective, than 2-Matsylsulfinyl-4-methyl-5-nitrotnazol, which is similar in structure and biological activity, is a well-known compound. Methods of testing. Tillage. The compositions of the test compound were prepared by suspending 15 mg of active substances in 20 ML / WATER1. 1 kg of soil contaminated with Pythfum spp (l) and Phlzoctonia solani (2) was mixed with this composition. Since (1) and {2 | successfully developed in the soil on the grains of the array and stalks of flax, then maize and stalks of flax traps were added to the soil. After 4 days at 20 ° C in the greenhouse, maize seeds and flax stalks were washed and placed on artificial culture medium consisting of 20 Bacto agar in water. After an incubation period of 24 hours, samples for the presence of fungi or were taken. the degree of their development. The table presents the results of experiments. The active formation of fungi was designated -. The partial formation was designated +. When the fungi on the culture did not develop, this indicated the effectiveness of the active substance, it was designated -. Seed processing Compositions of the test compounds were prepared by grinding them and mixing them in the required concentration with kaolin. The beet seeds were treated with these compositions in the amount of 6 g of the composition per kg of seeds, and then they were planted in podrni containing soil contaminated (I. After keeping for 3 weeks in a greenhouse at 1822 0 and a relative humidity of 70 I00%) healthy seedlings. Evaluation of activity against leaflets of fungi. Compositions of the studied compounds were prepared by dispersing these compounds in water in an admixture outside of a dispersant, for example, lignin sulfonate, and / or by wetting any agent, for example naphtalene sulfonate, and kilbenzenesulfonate, alkylpolyoxy- ethylene, or alkylarylpolyoxyethylenia. The culture to be protected from tomato downy powdery mildew, Phytophtog Infestans (G), was treated with this group by the method of pollination of young tomato plants about 10 cm high with the indicated active substance substances. indicated in Table 1. Gakim-treated plants were then infected (G) by experimenting ruthenium with an aqueous suspension containing 100,000 spores (3) per ml. After an incubation period of 4 days or 8 ° C and a relative humidity of 100%, the degree of development of the fungi was determined. During the incubation period, 166/8 hours of daylight was used.
    The results of processing are presented in the table. In this table, the concentration of the compounds used is indicated in 1 mg of active compounds of the compound per degree of protection against (3) opt-determined at these concentrations (HHx: 100% means total protection, 0% means no protection.
      .
    Young dwarf / French beans, about 10 cm high, against rust of Uromyces beans (4) were treated in the same way. Infection of plants was carried out with an aqueous suspension containing 300,000 spores (4) per) MP. The incubation period was 10 days at 18 ° C and a relative humidity of 100%.
    Evaluation in Uitro activity against plant-borne microorganisms.
    The HccneAyeNMe compounds were introduced into a culture medium consisting of 1.% by weight glucose, 0.2% by weight of yeast extract (marmite), 0.5% by weight of protein (peptone), 2.5% by weight agargar and 95.8% by weight % distilled water in petri dishes in concentrations
    ilO, 30 and 10Qh per 1 million. Petri dishes were infected with the pathogenic fungi Fusajirlum nivale (5), (2), Pythlum ulUmum
    (6) and pathogenic bacteria F.rwinla carotovora C7), and then held at. After 48 hours, the growth inhibitory effect of the compounds was determined yizalno. The results are presented in Table.,.
    Spraying with a water suspension Treatment against bacteria 2-tItilsulfiiil-3-nitro-4, 5-dimethylthiophene Processing Seed treatment Spraying with a slurry
    Treatment against bacteria (7)
    100 million
    100% shares 300 mg / l 100 ppm, shares 100 ppm 15 mg / kg soil 1500 mg / kg seed and 600 mg / kg seed 00 mg / l
    fungi
    (five)
    100 mpg
    100%
    Anti fungal treatment
    Anti fungal treatment
    Treatment against fungi
    .
    Tillage
    Spraying with water (3) suspension. (BUT)
    Thus, the described method allows to obtain new compounds.
    Table continuation
    100%
    (five)
    100 million shares
    (6)
    100%
    100 million shares
    (five)
    100%
    .100 ppm
    15 mg / kg
    (1) (2) soil
    300 mg / l
    possessing high Lungicidal and / or bactericidal activity.
    权利要求:
    Claims (2)
    [1]
    1. METHOD FOR PRODUCING NITROTHIOPHENE DERIVATIVES OF GENERAL FORMULA I
    R1 N0 z where R is Su C in alkyl, which may ; life £ is substituted by a Sualkoxycarbonyl group or thiocyanate group; or phenyl, pyridyl or N-hydroxypyridyl, which may be substituted with a nitro group, halogen or Su Sualkoxy group;
    1C is hydrogen, halogen, CyC & alkyl or phenyl;
    R 2 - hydrogen, Su С * in alkyl, cyano, Su Sualkanond ά Цо
    -alkylenedioxyalkyl, Su Cg -alkoxy · carbonyl oC -C ^ -Su hydroxyalkyl, ct-C ,, ~ C X -haloalkyl | C2 ~ Sualkoxycarboxyimidoyl group or CyCu-dialkylamino-sulfonyl group П “1 or 2, which is due to the fact that the compound of formula IT where R, 1C and R- 2 - have the indicated meanings, are subjected to oxidation. '
    [2]
    2. The method according to π.
    SI>
    类似技术:
    公开号 | 公开日 | 专利标题
    SU1050564A3|1983-10-23|Process for preparing derivatives of nitrothiphene
    KR860001001B1|1986-07-26|Process for the preparation of majusculamide c
    EP0105548A1|1984-04-18|Propynylaminoisoxazole derivatives
    RU2039036C1|1995-07-09|Biocidal composition and method of inhibiting growth of microorganisms in media
    WO1987003591A1|1987-06-18|Novel imidazole derivatives, bactericides containing them, and process for their preparation
    JPH0769814A|1995-03-14|Agronomical bacteria and fungi and method and composition for preventing, controlling and improving disease caused thereby
    CN106866600B|2018-08-17|The compound and its derivative of one class preventing and control Kiwi berry soft rot
    SU1450737A3|1989-01-07|Method of producing derivatives of 9.10-phenanthredione
    Tang et al.2018|p-Aromatic isothiocyanates: synthesis and anti plant pathogen activity
    US3214442A|1965-10-26|4, 5-dicyano-1, 3-dithiole-2-thione oxide and its preparation
    KR900006709B1|1990-09-17|Process for the preparation of sulf enylated acylhydrazones
    DE1670709A1|1970-12-03|Pesticides
    CA1043797A|1978-12-05|Water-soluble imidazole derivatives and a process for the preparation thereof
    CN103980223B|2016-11-09|2-substituent group-5-substituted anilinic-1,3,4-diazoles derivant and synthetic method thereof and application
    EP0238997B1|1990-06-20|Agricultural-horticultural fungicide
    CN109096209B|2022-03-01|Pyrazinamide compounds, preparation method and application thereof, and bactericide
    CN109666003B|2020-08-21|Pyrazinamide compound containing iodine element, preparation method and application thereof, and bactericide
    KR0146504B1|1998-08-17|Azoleamide derivatives
    JP2004051485A|2004-02-19|Agricultural use antimicrobial agent/fungicide comprising cinnamic acid derivative as active ingredient
    US3318767A|1967-05-09|Biocidal compositions containing 4, 5-dicyano-1, 3-dithiole-2-thione oxide
    KR830000377B1|1983-03-05|Preparation method of perhydroimidazo thiazole derivative
    EP0006633B1|1982-02-03|6-|perhydroimidazo|thiazole derivatives, antifungal compositions and a method of controlling fungal infections in plants
    KR0124984B1|1997-12-08|Oxazinyl azole derivatives
    WO2020047716A1|2020-03-12|Pyrazinamide compound, preparation method therefor and application thereof, and bactericide
    JPH07309703A|1995-11-28|Agricultural/horticultural germicide
    同族专利:
    公开号 | 公开日
    DK157299C|1990-05-07|
    BR8008235A|1981-07-07|
    EG14491A|1984-06-30|
    DK534780A|1981-06-20|
    YU317180A|1983-02-28|
    RO80925B|1983-04-30|
    EP0031173B1|1983-09-14|
    AU536144B2|1984-04-19|
    BG34756A3|1983-11-15|
    AU6543080A|1981-06-25|
    US4649154A|1987-03-10|
    AR227657A1|1982-11-30|
    PL125938B1|1983-06-30|
    EP0031173A1|1981-07-01|
    AT4643T|1983-09-15|
    HU188758B|1986-05-28|
    ES8200676A1|1981-11-01|
    IL61729D0|1981-01-30|
    CS221944B2|1983-04-29|
    ES497831A0|1981-11-01|
    DK157299B|1989-12-04|
    US4451660A|1984-05-29|
    RO80925A|1983-04-29|
    NZ195851A|1983-09-30|
    IL61729A|1986-08-31|
    CA1150264A|1983-07-19|
    DE3064846D1|1983-10-20|
    PL228509A1|1982-02-01|
    ZA807898B|1982-07-28|
    DD155384A5|1982-06-09|
    JPS5697282A|1981-08-05|
    JPH0249281B2|1990-10-29|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2389128A|1941-12-13|1945-11-20|Parke Davis & Co|Sulphones and method of preparing same|
    US2562988A|1948-12-18|1951-08-07|Texas Co|Nitro-and thiocyano-substituted thiophene compounds|
    US3682968A|1969-06-25|1972-08-08|Merck & Co Inc|Anti-inflammatory salicylic acid derivatives|
    JPS526563B2|1972-04-24|1977-02-23|
    EP0031173B1|1979-12-19|1983-09-14|Duphar International Research B.V|New nitrothiophenes, method of preparing the new compounds, as well as fungicidal and/or bactericidal compositions on the basis of the new compounds|EP0031173B1|1979-12-19|1983-09-14|Duphar International Research B.V|New nitrothiophenes, method of preparing the new compounds, as well as fungicidal and/or bactericidal compositions on the basis of the new compounds|
    EP0234622B1|1986-02-19|1990-06-27|Duphar International Research B.V|New thio compounds having fungicidal activity|
    EP0273602A1|1986-12-05|1988-07-06|Eli Lilly And Company|3-Cyano-4-arylthiophenes|
    DE3812177A1|1988-04-13|1989-10-26|Bayer Ag|2-PHENYLSULFINYL-NITRO-PYRIDINE, METHOD FOR THE PRODUCTION AND THEIR USE|
    TW319681B|1995-09-01|1997-11-11|Rohm & Haas|
    DE19540951A1|1995-11-03|1997-05-07|Basf Ag|Water-absorbent, foam-like, crosslinked polymers, processes for their preparation and their use|
    DE19607529A1|1996-02-28|1997-09-04|Basf Ag|Absorber element of superabsorbent foams with anisotropic swelling behavior|
    DE19809540A1|1998-03-05|1999-09-09|Basf Ag|Water-absorbent, foam-like, crosslinked polymers, processes for their preparation and their use|
    US7220821B2|2002-02-04|2007-05-22|Basf Aktiengesellschaft|Process for the reduction of the residual monomer content of water-absorbent foam|
    WO2010114881A1|2009-04-01|2010-10-07|Progenra Inc.|Anti-neoplastic compounds, compositions and methods|
    GB201514021D0|2015-08-07|2015-09-23|Arner Elias Set Jeno|Novel Pyridines and their use in the treatment of cancer|
    WO2018146468A1|2017-02-07|2018-08-16|Oblique Therapeutics Ab|Sulfinylpyridines and their use in the treatment of cancer|
    MA47452A|2017-02-07|2019-12-18|Oblique Therapeutics Ab|HETEROCYCLYLSULFONYL SUBSTITUTION PYRIDINES AND THEIR USE IN CANCER TREATMENT|
    JP2020506970A|2017-02-07|2020-03-05|オブリーク セラピューティクス アーベー|Hydrocarbylsulfonyl-substituted pyridines and their use in treating cancer|
    MX2019009351A|2017-02-07|2019-09-19|Oblique Therapeutics Ab|Heteroarylsulfonyl-substituted pyridines and their use in the treatment of cancer.|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    NL7909124|1979-12-19|
    [返回顶部]