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    • 专利摘要:
    Substituted 2,6-dinitrobenzenamines having a chlorine atom in the 3-position and of the following formula are described …<CHEM>… wherein… X is chloro, fluoro, or bromo;… m, p, and s are individually 0 or 1;… n is 0, 1 or 2;… q and r are individually 0, 1, 2, or 3;… the sum of m, n, p, q, r, and s is 1 to 3; with the proviso that when n is 2, then m, p, q, r, and s are all 0, and the trifluoromethyl groups must be in the 3- and 5-positions; with the further proviso that when s is 1, m and p both are 0, and the sum of n, q, and r is not 0; and with the further proviso that q is 1 only when the sum of m, n, r, and s is not 0. The compounds of formula I are prepared by a process comprising reacting the compound of the formula …<CHEM>… with an appropriate aniline in the presence of an acid scavenger. The compounds are active as fungicides. Compositions comprising a compound of formula I and methods of application are described.
    公开号:SU990080A3
    申请号:SU792714351
    申请日:1979-01-29
    公开日:1983-01-15
    发明作者:Аллен Дрейкорн Барри
    申请人:Эли Лилли Энд Компани (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD OF OBTAINING SUBSTITUTES. 2,6-DINITROBENZOLAMINE
    This invention relates to a process for the preparation of new derivatives of 2, b-dinitrobenol-olamines having a chlorine atom in the 3-position, which can be used as fungicides.
    A method of obtaining derivatives of 4-trifluoromethyl-2,6-dinitrobenzene amines of the formula
    Tto
    (
    // L -NH - //.
    (SG, p 7
    1. ОгН where (a) Q is a cyano or trifluoromethyl group, X is a halogen atom; m 0-3; p 0-1; p, q 0-3, amount. ha, p, p, and q is from 2 to 5, (b) is a nitro group and X is a halogen atom, m is 0-3, n is 0-1; p 0-2; q 0-3 and the sum of pir is equal to rt3; the sum of m, n and q is 2-5.
    These compounds are prepared by reacting a compound of formula
    with compound of formula
     Yat jC (5 Y e E
     (SG5) p. (BEFORE)
    where Y is a halogen atom, and Q, X, m, n, p and to q have the indicated value. These compounds possess fungicidal activity, but are toxic to various insect and other invertebrate tl3 pests. 5 The purpose of the invention is to expand the range of compounds with fungicidal activity, which exhibit increased activity, reduced phototoxicity and reduced mammalian toxicity.
    The goal is achieved by the fact that in the method of obtaining derivatives of 2,6-dinitrobenzene amines of the formula I
     NG
    (MjIjTV

    152 ° C, yield 12.2 g, from 10.6 g of 2,6-dichloraniline and 20 g of 2,4-dichloro-3,5-dinitrobeneotrifluoride.
    Calculated% C 36.27, H 1.17, N 9.76.
    Чз 5СззМз04 Found,%: C 36.42, H 1.15, N 8.75.
    Example 8. 3-Chloro-M- (2,5-dibromophenyl) -2,6-dinitro-4- (trifluoromethyl) -benzolamine, having a TL 176177 C and a yield of 2.5 g from 16.3 g 2, 5-di-Yu-bromoaniline and 20 g of 2,4-dichlor-3,5-dinitrobenzotrififter.
    Calculated,%: C 30.06, H 0.97, N 8.09.
    e sN5S1Vg2RzMz04-15
    Found,%: C 30.24, H 0.78,
    N 7.83.
    Example 9. 3-Hop-N- (2,6-dibromophenyl) -2,6-dinitro-4- (trifluoromethyl) -benzolamine, having a melting point of 164-20 165 ° C, yield of 14.6 g from 16.3 g 2,6-dibromaniline and 20 g 2,4-dichloro-3,5-dinitrobenzotrifluoride.
    Calculated,%: C 30.06, H 0.97, N 8.09.25
     HcBrjClFaMiO.
    Found,%: C 30.11, H 0.96, M 8.11.
    PR, and mep 10. 3-Chloro-N-12,4-dibromophenyl) -2,6-dinitro-4- (trifluoro p methyl) -benzolamine, having MP 122-123 and yield 5.5 g from 16.3 g of 2,4-dibroman y1Ina and 20 g of 2,4-dichloro-3, 5-dinitrobenzofluoride.
    Calculated,%: C 30.06, H 0.97. N 8.09.
    С1зН5Вг2С1РзН, 04.
    Found,%: C 30.07, And 1.10, N 8.24.
    Example 11. 3-Chloro-2,6-dinitpo-N-I2, 4-trichlorophenyl) -4- (trifluorome-O-type) -benzenamine, having mp 144145 C, yield 10.5 g from 12.8 g 2.4 , 5-trichlorohydrin and 20 g of 2,4-dichloro-3, 5-dinitroboz nontrifluoride.
    Calculated, C 33.58, H 0.87.45
    N 9.04.
    .
    Found,%: C, 33.87; H, 1.17,. N 8,97. Example 12. W-Chloro-2,6-dinitro-N- (C / 4,5-trichlorophenyl) -4- (trifluoromethyl) -benzolamine, having a TPD of 186-187 ° C and a yield of 12.6 g of 12.8 g of 3,4,5-trichloroaniline and 20 g of 2,4-di-55-lor-3,5-dinitrobenzotrifluoride.
    Calculated,%; C 33.58, H 0.87, 9.04.
    With zN4S14RzNz04.
    Found,%: C, 33.86; H, 0.97; 60, 9.21.
    Example 13. 3-Chloro-2,6-diitro-M- (2-nitrophenyl) -4- (trifluoromethyl) -benzolamine, having 136137 ° C and a yield of 7.05 g from 9 g of 2-nitro O 65
    aniline and 20 g of 2; 4-dkhl6p-3,5-diniT robenzotrifluoride.
    Calculated: C 38.40, H 1.49, N 13.78.
    C ..
    Found% J C 38.66, And 1.47, N 13.67.
    PRI me R. 14. 3-Chloro-2,6-dinitro-N-phenyl-4-trifluoromethyl) -benzolamine, having a TC.r. 128-130 C and a yield of 2.5 g, from 15.25 g of aniline and 50 g of 2.4 -dichlor-3, 5-dinitrobenzotrifluoride.
    Calculated,%: C 43.17, H, N 11.62.
    C.H CIFgNiO.
    Found: C, 43.41; H, 2.16; N, 11.41.
    Example 15. 3-Chloro-H- (2-chloro-4-nitrophenyl) -2,6-dinitro-4- (trifluoromethyl) -benzolamine, having a T in 141-142 ° C of 11.2 g of 2-HLOR- 4-NITroanilina and 20 g of 2,4-dichloro 3, 5-dinitrobenzotrifluoride.
    Calculated:% C 35.40, H 1.14, N 12.70.
    With cndscrzm o
    B
    35.43, and 1.13, Naida
    Found,%: N 12.43.
    Example 16. M- (2-Bromo-4-nitrophenyl) -3-chloro-2,6-dinitro-4- (trifluoromethyl) -benzolamine, having 144-145 C, yield 6.5 g from 14.1 g 2 -bromo-4-nitroanil-a and 20 g of 2,4-dichloro-3, 5-dinitrobenzotrifluoride.
    Calculated,%: C 32.16, H 1.04, N 11.54.
    C jHjBrClFjN Ofc.
    Found,%: C 32.25, H 1.27, N 11.7
    Example 17. 3-Chloro-K- (2,6-dichloro-4-nitrophenyl) -2,6-dinitrog. -4- (trifluoromethyl) -benzolamine, having a melting point of 176-177 ° C and a yield of 5.9 g of 13.45 g of 2,6-dixJfop-4-nitroaniline and 20 g of 2,4-dichlrr-3, 5-dinitrobenzotrifluoride.
    Calculated,%: C 32.83, H 0.85, N 11.78.
    t, 5H Cl3F3N406 ..
    Found,%: C 33.05, H 1.02, / N.
    Example 18. 3-Hlorop-N-2,4-d50 | fluorophenyl) -2,6-dinitpo-4- (tryptermomethyl) benzene amine, having a melting point of 111-112®С and yield of 6.8 g from 8.4 g 2,4-difluoroaniline and 20 g 2,4-dichloro-3, 5-dinitrobenzotrifluoride.
    Calculated,%: C 39.25, H 1.26, N 10.56. ,
    With NZS RuChZO.
    Found,%: C 39.53, H 1.54, N.10.41.
    Example 19. 3-Chloro-M-3,4-dichlorophenyl) -2,6-dinitro-4- (trifluoromethyl) -benzoalami n.
    A solution of 21.2 g (0.130 mol) of 3,4-dichloraniline and 20 g (0.065 mol) of 2,4-dichloro-3/5-dinitrobenzene trifluoride in 250 ml of ethanol is refluxed for 4 days. The reaction mixture is cooled, and the solid which is obtained during cooling is filtered and dried. The solid is recrystallized from ethanol to obtain substances with Trl 152-153 ° C and identified as 3-chloro-1 - (3,4-dichlorophenyl -2, b-dinitro-4- (trifluoromethyl) benzene amine. Calculated,%: C 36.27, H 1.17, N 9.76. C 1 H 2 C 1 C R 3 H 3. Found: C, 36.35, H 1.33, N 9.91. Following the procedure described in Example 19, other compounds listed in the following examples were prepared. EXAMPLE 20 3-Chloro-2,6-M- (4-nitrophenyl) -4- (trifluoromethyl) -benzolamine having T; pd 207-208 yield 12 g of 18 4-nitroaniline and 20 g of 2,4-dichloro-3, 5-dinitrobenzo trifluoride. Calculated: C 38.40, H 1.49, No. 13.78. CH CIFgN Ofe. C 38.66, H 1, 67, Found,%: N 13.88. EXAMPLE 21 H-Chloro-N- (3,4-dibromophenyl) -2,6-dinitro-4- (methyl trift) -benzolamine having T ,, 1 167 ° С, yield 2.4 g from 5 g of 3,4-dib o aniline and 3 g 2,4-dichloro-3, 5-dinitol of benzotrifluoride. Calculated,%: C 30.03, H 0, 97, N 8.09. H Br ClF-jN O. Found: C, 30.25; H, 1.09; N8.06. Example 22. 3-Chloro-2,6-din-ro-4- (trifluoromethyl) -N-4-Chtrifluoromethyl) phenylJ-benzamine, having a temperature of 154-155 ° C, yield 8.25 g out of 12 4 -aminobenzotrifluoride and 11.35 g of 2,4-dichloro-3, 5-dinitrobeneotrifluor da. Calculated,%: C 39.14, H 1.41, N 9.78. С-, 4НбС1РбМз04, С 39.37, H 1.55, Found,%: N 9.90. Example 23. 3-Chloro-2,6-dinitro-4- (trifluoromethyl) {methyl methyl) -phenylJ-benzolamine having an IT melt of 159-160 ° q, yield 8 g from 12 g 3-aminobenzotrifluoride and 11.35 g 2,4-dichloro-3,5-dinitrobenzotriffer "" Calculated,%: C 39.14, H 1.14, N 9.78. . Found,%: C 39 ,, H 1.36, N 9.77. Example 24. 3-Chloro-H- 4 (cyanomethyl) -phenyl -2,6-dinitro-4 (trifluoromethyl) -benzolamine, having rl 173-174C, yield 13 g from 13.2 4-cyanomethylaniline and 15.25 g 2,4dichloro-3, 5-dinitroben zotrifluoride. Calculated,%: C 44.96, H 2.01, 13.98. CijHsClFjN O .. Found,%: C 45.18, H 2.17, N 14.14. Example; 25. Nt.2-Brom-4-methylphenyl} -3-chlorop-2, 6-dinitpo-4- (trifylmethyl) -benzolamine, having a melting point of 119-120C, yield 5 g from 9.3 g of 2g-bromo-4-toluidine and 7.6 g of 2,4-dichloro-3, 5-dinitrobenzotrifluoride. Calculated,%: C, 36.99, HI, 77, N, 9.24. With zNdVgSGRZMzO. Found,%: C 37.24, H 2.05, N 9.54. Example 26. 3-Chloro-N-3-cyanophenyl) -2,6-dinitro-4- (t rifluoromethyl) -benzolamine, having a melting point of 147149 ° C, yield 4.3 g from 4.72 g. 3-aminobenzonitrile and 6.1 g of 2,4-dichloro-3, 5-dinitrobenzotrifluoride. Calculated,%: C 43.49, H 1.56, N 14.49. Ci4HbClF3N 04. H 1.77, Found,%: C 43.71, N 14.46. Example 27. 3-Chlbp-N- {4-cyanophenyl) - 2,6-dinitro (trifluoromethyl) -benzolamine, having T p ,, 179181 С from 2.36 g of 4-cyanoaniline and 3 g of 2,4-dichloro -3, 5-dinitrobenzotrifluoride. Calculated,%: C 43.49, H 1.56, 14.49. C NlS1R Mz04C 43.37, H 1.81, Found,%: 14.17. 28. 3-Chloro-N-C4-chloro; Example-3- (trifluoromethyl) -phenyl 3-2,6-dinitro-4- (trifluoromethyl) -benzolamine, having Mp 169-170 0, yield 16.45 g from 25 g 5-amino-2-chlorobenzotrifluoride and 19.5 g of 2,4-dichloro-3, 5-dinitrobenzotrifluoride. Calculated,%: C 36.23, H 1.09, N 9.05. , 0., Found,%: C 35.95, H 1.02, N 9.24. Example 29. 3-Chloro-2,6-diHHTpo-N- (3,5-dinitrophenyl) -4- (trifluoromethyl) -benzenamine. A mixture of 1.83 g (0.01 mol) of 3,5-dinitroaniline, 3.05 g (0.01 mol) of 2,4-dichloro-3, 5-dinitrobenzotrifluoride, 0.53 g of sodium carbonate and 20 ml of dimethylformamide is heated on the steam bath for 4 days. Thereafter, sodium carbonate is further added to the reaction mixture and heating is continued for 2 days. The reaction mixture is treated by pouring it into water and acidifying the mixture with a dilute aqueous acidic solution and extracting with methylene dichloride. The methylene dichloride layer is dried, the drying agent is filtered off and the filtrate is concentrated in vacuo. The residue was dissolved in methylene chloride and chromatographed on silica gel. The fractions were combined and evaporated, and the residue was recrystallized from ethanol to give the product, the melting point being 188-189 ° C, and identified as 3-chloro-2,6-dinitro-N- (3,5-dinitrophenyl) -4- (trifluoromethyl) -benzolamine. Yield 0.65 g. Calculated,%: C 34.57, H 1.12, N 15.51. :. With zNzSRZN Od. Found,%: C 34.83, H 1.22, N 15.74. Following the procedure indicated in Priory 29 g, other compounds were obtained, given in the following examples. Example 30. N- (2-Bromo-4,6-dinitrophenyl) -3-chloro-2,6-dinntro-4-trifluoromethyl) -benzo1Gamin, having a melting point of 144-146 ° C, yield 1.3 g out of 5, 24 g of 2-bromo-4,6-dinitroaniline and 6.1 g of 2,4-dichloro-3,5-dinitrobenzotrifluoride. Calculated,%: C 29.43, H 0.76, N 13.20. C 3H4BrtlF3N508. Found,%: C 29.68, H 0.97, N 13.05. Example 31, 5-bis (Trifluoromethyl) phenyl-3-chloro-2,6-dinitro-4-1 trifluoromethyl) -benzenamine. A mixture of 15 g (0.066 mol) of 3,5-bis (trifluoromethyl Danilin, 100 ml of n-butanol, 20 g (0.066 mol) of 2,4-dichloro-3, 5-dinitrobenzotrifluoride and 11 ml of triztilamine is placed in a 250 ml flask with a boil t under reflux for 48 h. The reaction mixture is cooled and the solvent is distilled off in vacuo. The residue is recrystallized by chromatography on a silica gel column using toluene as eluent. The fractions are concentrated in vacuo and the combined residue is recrystallized from ethanol. iknday 156-158 0. Product identific irovanny as N-3,5-bis7- (trifluoromethyl) -phenyl-3-chloro-2,6-di-. nitro-4g (trifluoromersh1) -benzolamine. Yield 3.2 g. Calculated,%: C 36.20 , H 1.01, N 8.76. With BN5C RvNs04. Found, Chg C 36.37, H 0.97, N 9.91. For use as a func. G-icide, the described compounds can be formed into new compositions, 11990080 Continuation of table 2 Continuation of tvb71itsK. 13 I demonstrate the interaction of aniline of the formula | I, jHt In V t 4lA4.y4-k. (e Lt, - CLS5 "H AdrJ oOi (Ot1l) p tJ spiro-D in the presence of an acid acceptor, 990080 1 .4 such as sodium carbonate or triethylamine. Sources of information taken into account in the examination of US Patent 3,950,377, C. 260 -465, published in 1976.
    权利要求:
    Claims (2)
    [1]
    Claim
    The method of obtaining substituted
    [2]
    2,6-dinitrobenzene amines of the formula u (Oilflr where X is chloro or bromo; t, p and S are each 0 or 1, η = 0.1 or 2; is an integer from 0 to 3, g = 0.1 or 2, · The sum of m, n, p, q, g and S is in the range from 1 to 3; provided that when η is 2, then c, p, q, g and S are all 0 and the trifluoromethyl group must be in 3 and 5-positions, and also under the condition when S is 1, then p both are 0 and the sum of n, q and r is not 0, and when m, p, q and S are 0, and r is 2, then n = 0 or 2, and also q is 1 only when the sum of w, n, r and S is not equal to 0, namely that the compound of formula II
    1 L is reacted with an aniline derivative of formula 111 in the presence of an acid acceptor such as sodium carbonate or triethylamine.
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    同族专利:
    公开号 | 公开日
    FR2415619B1|1980-11-14|
    GB2013197A|1979-08-08|
    EG13874A|1982-09-30|
    GT197955866A|1980-07-11|
    US4152460A|1979-05-01|
    PT69086A|1979-02-01|
    IL56443D0|1979-03-12|
    BE873550A|1979-07-18|
    GR72749B|1983-12-02|
    NZ189410A|1980-09-12|
    DD141772A5|1980-05-21|
    MX5371E|1983-06-30|
    BR7900462A|1979-08-21|
    CH635568A5|1983-04-15|
    ATA60779A|1980-11-15|
    ZA79344B|1980-01-30|
    AU525301B2|1982-10-28|
    IE47988B1|1984-08-22|
    GB2013197B|1982-07-14|
    PH15211A|1982-09-27|
    LU80828A1|1979-06-05|
    PL212966A1|1979-08-27|
    FI66348C|1984-10-10|
    JPS54109931A|1979-08-29|
    EP0003430B1|1982-01-06|
    ES477214A1|1980-03-01|
    CS201022B2|1980-10-31|
    AT362962B|1981-06-25|
    FI790141A|1979-07-31|
    AR223472A1|1981-08-31|
    AU4372779A|1979-08-09|
    IE790153L|1979-07-30|
    FR2415619A1|1979-08-24|
    CA1117548A|1982-02-02|
    FI66348B|1984-06-29|
    PL117491B1|1981-08-31|
    DK36479A|1979-07-31|
    DE2961728D1|1982-02-25|
    HU181430B|1983-07-28|
    EP0003430A1|1979-08-08|
    RO76486A|1981-04-30|
    IL56443A|1982-05-31|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3764624A|1970-08-05|1973-10-09|United States Borax Chem|N-substituted-2,6-dinitro-3--4-substituted-aniline compounds|
    US3950377A|1972-12-20|1976-04-13|Imperial Chemical Industries Limited|Diphenylamine derivatives|
    GB1405120A|1972-12-20|1975-09-03|Ici Ltd|Nitrobenzene derivatives|US4259347A|1978-02-16|1981-03-31|Eli Lilly And Company|Control of phytopathogens using dinitroaniline compounds|
    US4309425A|1979-08-24|1982-01-05|E. I. Du Pont De Nemours And Company|Miticidal, insecticidal, ovicidal and fungicidal N-sulfonamides|
    IL61776A|1980-01-08|1984-05-31|Lilly Co Eli|N--polyfluoroethoxy-benzenamines,their preparation,fungicidal and anticoccidial methods using them|
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    CN108976167B|2017-06-02|2021-12-07|沈阳中化农药化工研发有限公司|Substituted phenylhydrazine compound and application thereof|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/873,190|US4152460A|1978-01-30|1978-01-30|3-Chloro-2,6-dinitro-N--4-benzenamines|
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