• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    The invention relates to hydroxyl-amino compounds, in particular to the preparation of hydroxylamine derivatives (PHA) of the general formula ArONHj, where Ar is phenyl containing, in addition to 1-2 nitro groups, halogen, lower alkyl or alkoxyl or Ar-nitroquinolyl, which possess inhibiting the effect of oxygen on photosynthesis properties and can be used in agriculture. The purpose of the invention is to develop a method for obtaining new more active compounds of the indicated class. The preparation of PHA is carried out by the interaction of a compound of the formula ArHal, where Ar is indicated, Hal is a halogen with hydroxylamine hydrochloride in an aqueous-alcoholic medium in the presence of an alkali. Tests show that PHA exhibits higher activity as a growth factor, no toxicity is detected. 1 tab. I (U)
    公开号:SU1428190A3
    申请号:SU843703418
    申请日:1984-02-10
    公开日:1988-09-30
    发明作者:Тессье Жан；Жиро Пьер；Эрве Жан-Жак；Жак Ван Ассш Шарль
    申请人:Руссель Юклаф (Фирма)；
    IPC主号:
    专利说明:

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    The invention relates to a method for producing new hydroxylamine derivatives having valuable properties inhibiting the action of oxygen on photo synthesis and which can be used in agriculture. .
    The purpose of the invention is a method for producing new derivatives of amine hydroxyls, which have the ability to inhibit the action of oxygen on photosynthesis and the ability to enhance plant growth.
    Compounds with these properties have not been previously described in this series.
    The following examples illustrate the proposed method and the biological activity of the compounds obtained.
    Example 1, 0- (2-Methyl-4-nitrophenyl) -hydroxylamine.
    8.35 g of hydroxylamine hydrochloride are mixed in 84 ml of water and 15.5 g of 2-fluoro-5-nitrotoluene in 84 ml of ethanol. Then, 22 ml of a solution of sodium hydroxide (400 g / l) are introduced at 15 ° C for 15 minutes. The temperature is allowed to rise to 20 ° C and stirred for 17 hours. The reaction mixture is poured into water, extracted with methylene chloride, washed with water, the organic layer is dried and evaporated to dryness. 1.1 g of the desired boro 35 product were obtained after chromatography on silica, eluting with methylene chloride (m.p.).
    Synthesis of 1 similar 2-fluoro-5-nitro toluene, 40
    30 g of 2-fluorotoluene are cooled down for 2 hours, 22 ml of nitric acid are added. Stir for 1 hour at -15 ° C and allow the temperature to rise to 20 ° C. The reaction mixture 45 is drunk on ice. Extracted with ether, washed with water, dried the organic layer and evaporated to dryness. After rectification, 34.4 g of the expected product are obtained. Bp 100-101 With CQ (10-11 mm Hg).
    . Example 2. 0- (4-1-1 nitro-3-methoxyphenyl) hydroxylamine.
    A mixture of 10 g of 2-nitro-5-fluoroanisole, 38 ml of ethanol, 38 ml of water, 4.88 g of hydroxylamine hydrochloride is cooled to. At this temperature, 13 ml of 10 N are introduced within 15 minutes. caustic soda solution. After completion of the addition of caustic soda, the temperature is allowed to rise to 20-25 ° C. The mixture is kept under stirring for 6 hours at room temperature and the precipitate formed is filtered off with suction and dried. The product obtained is recrystallized from methanol, filtered off with suction, dried, and 5.85 g of the expected product is evaporated, m.p. 106-107 s.
    Synthesis of 2-nitro-5-fluoroanisole.
    12.6 g of 3-fluoro anisole are dissolved in 100 ml of acetic anhydride. The mixture is cooled to -5-0 ° C and a mixture of 32 ml of nitric acid and 95 ml of acetic anhydride is added dropwise with stirring. The reaction mixture is kept under stirring for 1 h at 0-5 C. The reaction mixture is hydrolyzed, poured onto ice. The precipitate that forms is filtered off and dried. Thus receive 6, 77 of the target product (t "pl. 50 s).
    Example 3. 0- (2-Chloro-4-nitrophenyl) hydroxylamine.
    For 5 minutes at 5 ° C, a solution of 8.5 g of hydroxylamine hydrochloride in 85 ml of WATER was introduced. B a mixture of 17.3 g H-chloro-4-fluoronitrobenzene and 170 ml
    E tanola. Then add 22 ml of Yun sodium hydroxide solution. Stir 8 h at, add 100 ml of water and suck off the resulting suspension. The precipitate is washed with water and dried under vacuum. 9 g of product are obtained, which is purified by recrystallization from methanol. Thus obtained 7.6 of the target product with so pl. 125-126 ° C.
    Synthesis of 3-chloro-4-fluoronitrobenzene.
    120 ml of dimethyl sulfoxide, 3 ml of benzene and 35 g of potassium fluoride are mixed, and then 50 g of 3,4-dichloronitrobenzene are added. The mixture is heated at 180-185 ° C with stirring for 2 hours. Distilled with water vapor and extracted with distillate isopropyl ether. The organic layers are combined, dried and distilled in vacuo (3-4 mm Hg at 40 ° C. The distillate obtained is rectified under a vacuum of 15 mm Hg). Obtain 29 g of the target product with so pl. 41 - 43 s.
    Example 4, C1- (2-Nitro-4-x-pore phenyl) hydroxylamine.
    With stirring, a solution of 8.7 g of 2-fluoro-5-chloronitrobenzene in 85 ml of ethanol. 4.4 g of hydroxylamine hydrochloride are added to 45 ml of water. 11 ml Yun is added. caustic soda solution. Then stirred for 6 h at 20 ° C. 45 ml of water are added, the precipitate is filtered off with suction and washed with water. The precipitate is extracted with methylene chloride, the organic compounds are combined, the layers are washed with water, dried and distilled under vacuum at 40 ° C / 3-4 mm Hg. 2.1.1 g of the expected product is obtained. 125-12b C.
    Synthesis of 2-fluoro-5-chloronitrobenzene.
    A mixture of 120 ml of dimethyl sulfoxide, 80 ml of benzene, 35 g of potassium fluoride and 50 g of 2,5-dichloronitrobenzene is heated with stirring at 140 ° C and then heated at 180-185 ° C for 3 hours. The mixture is cooled and distilled with steam. . The distillate is extracted with isopropyl ether. Combine the extracts, dry them and distill at 40 ° C / 14 mm Hg. Obtain 10.1 g of the target product (pc 1,5558).
    Example 5. 0- (5-Nitro-8-quinolyl) hydroxylamine.
    9.6 g of 8-fluoro-5-nitroquinoline, 300 ml of methanol and 4.4 g of hydroxylamine hydrochloride are heated at 40 ° C with stirring. The resulting solution is cooled to 5 ° C and injected over 30 minutes at 5-10 ° C 11 ml of 10N sodium hydroxide solution. Stir for 6 h at 20 ° C. The mixture is suction filtered, the precipitate is extracted with methylene chloride, dried and distilled in vacuo. Obtain 1.6 g of the target product with so pl. 228-230 ° С
    Synthesis of 8-fluoro-5-nitroquinoline.
    30 ml of concentrated sulfuric acid are cooled to -5 ° C, stirred and 15 ml of nitric acid are added. Then, at -5-0 ° C, 16 g of 8-fluoro-quinoline is introduced with stirring for 30 Mits. The reaction mixture is then stirred for 3 hours at 0 ° C, and the mixture is allowed to warm to room temperature. Stir for 2 hours at this temperature. It is introduced into a mixture of water and ice, the precipitate obtained is sucked off, introduced into water and alkalized with a 10% solution of sodium carbonate. Extracted with methylene chloride, dried and evaporated to dryness. 12 g of the expected product are obtained (mp. 132-133 ° C).
    The compounds of the following examples are prepared analogously:
    6. from 4-nitro-2-bromo-1-fluorobenzene - 0- (4-nitro-2-bromophenyl) hydroxylamine, m.p. 122 ° C; .
    7.From 4-nitro-3-methyl-1-fluorobenzene - 0- (4-nitro-3-methylphenyl) hydro
    roxylamine, m.p. 100 C;
    8. from 4-nitro-3-bromo-1-fluorobenzene - 0- (4-nitro-3-bromophenyl) hydroxylamine, m.p. 95 C;
    9. From 4-nitro-1, 2-difluorobenzene- O- (4-nitro-2-fluorophenyl) hydroxylamine, m.p. 125 ° C;
    10.From 4-nitro-2-fluoro-1-carboxybenzene - 0- (2-nitro-4-carboxyphenyl) hydroxylamine, m.p.
    11. From 2-fluorobenzothiazole - 0-ben zothiazolylhydroxylamine, m.p. 185 - 86 ° C,
    12. From 2-nitro-3-fluoro-1-ethoxycarbonylbenzene — 0- (4-nitro-3-ethoxycarbonylphenyl) hydroxyl gan, mp. 92 C;
    13. From 4-nitro-2- (l-RS-hydroxyethyl) -1-fluorobenzene - O-14-nitro-2- - (1-K3-hydroxyethyl) phenyl hydroxylamine, m.p. 120 ° C;
    14. From 5-nitro-2-fluoro-1-ethoxycarbonylbenzene - 0- (4-nitro-2-ethoxycarbonylphenyl) hydroxylamine, t, pl. 116-117 ° C;
    15. From 5-nitro-2-fluoro-1-diethylcarbamoylbenzene - 0- (4-nitro-2-diethylcarbamoyl) hydroxylamine, mp. 139-140 ° C;
    16. From 4-nitro-1-fluorobenzene - O- (4-nitronaphthyl-1) hydroxylamine, m.p. 108-110 ° C;
    17. From 5-nitro-2-fluoro-1-methoxy-carbonylbenzene — 0- (4-nitro-2-methoxycarbonylphenyl) hydroxylamine, m.p. 175-180 ° C;
    18. From 5-nitro-3-fluorobenzeneamine - O- (4-nitro-3-aminophenyl) hydroxylamine, m.p. 190 191 ° C;
    19. From 3-nitro-3-fluoro-1-ethoxycarbonylbenzene, 0- (4-ethoxy-2-nitrophenyl) hydroxylamine, m.p. 102 C;
    20. From 2-nitro-5-fluoro-1-allyloxybenzene - 0- (4-nitro-3-alyloxyphenyl) hydroxylamine, m.p. 94-95 ° C;
    21. From 4-acetyl-2-nitro-1-fluorobenzene to 0- (4-acetyl-2-nitrophenyl) hydroxylamine, m.p. 132 C;
    22 "from 2-nitro.-5-fluoro-1-acetylaminobenzene - 0- (4-nitro-2-acetyl-aminophenyl) hydroxylamine, m.p. 150 С
    23.i-3 2,4-dinitro-5-methyl-1-fluorine benzene - 0- (2g4-dinitro-5-methylphenyl) hydroxylamine, m.p. 105 ° C;
    24. From 4-nitro-3-n-pentstoxy-1- -fluorobenzene - 0- (4-nitro-3-n-pentnloxyphenyl) hydroxylamine, m.p. 78-79 s;
    25.From 4-nitro-3-isopropyloxy-1-fluorobenzene — 0- (4-nitro-3-isopropyloxy) hydroxylamine, m.p. SA C;
    26. From 4-nitro-3-ethoxy-1-fluorobenzene - 0- (4-nitro-3-ethoxyphenyl) hydroxylamine, m.p. 97 98 ° C;
    27. From 4-nitro-3-n-butyloxy-1- -fluorobenzene - 0-4 (-nitro-3-n-buty-
    loxyphenyl) hydroxylamine, so pl. 75 - 760С.
    Synthesis of starting 3-nitro-4-fluorobenoic acid.
    150 ml of nitric acid (density 1.42) are poured to 300 ml of concentrated sulfuric acid cooled to 0 ° C. The reaction mixture was kept at 0 ° C and 50 g of p-fluorobenzoic acid was added in 30 minutes. Stir for 1 hour at 0 ° C and allow the temperature to rise until then stirred at this temperature for 16 hours. The reaction mixture is poured onto ice, sucked off, washed and the resulting precipitate is dried. Obtain 47.6 g of the target product (mp. 123-124 C).
    Synthesis of 3-bromo-4-fluoro-1-nitrobenzene.
    At 20 ° C, 28, 2 g of p-fluoronitrobenzene and 10.4 ml of bromine are mixed. The mixture is cooled to 0 ° C and 20 ml of water and 180 ml of concentrated sulfuric acid are slowly added. Then add 34 silver sulfate. The temperature is allowed to rise to -20-25 ° C and stirred for 16 hours. The reaction mixture is drunk in water, the insoluble matter is sucked off, washed with water and methylene chloride. Decanted, the filtrate is extracted, washed with water and dried with magnesium sulfate, the filtrate is evaporated to dryness. The product is dissolved in isopropyl ether and crystallized.
    Thus, 8.2 g of the expected product are obtained. .
    Similarly, the following non-desired products are obtained: 4-nitro-3-methyl-1-fluorobenzene from 3-methyl-1-fluorobenzene, 4-nitro-3-bromo-1-fluorobenzene (mp. 42) from 3-bromo. -1-fluorobenzene, 4-nit
    Ro-1,2-difluorobenzene (so kip. 80 ° C / 10mm55 ° thionyl, excess thionyl merc., distilled off) from 1,2-difluorobenzene; -Ni chloride and distilled several times
    tro-3-ethoxycarbonyl-1-fluorobenzene in a vacuum. The acid chloride is obtained, which (mp 50 ° C) is poured from 4-nitro-3-carboxylate into 400 ml of methanol. Po-1-fluorobenzene (so pl. 139 ° C), which is obtained by stirring the solution
    0 5
    ABOUT
    Q. five
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    ry on / 7yuchen. from 3-fluorobenic acid ..
    Synthesis of 3-fluoro-4,6-dinitrotoluene ..
    The solution of 30 g of metafluorotoluene in 60 mp of sulfuric acid is cooled to -15 ° C. 30 ml of nitric acid (density 1.49) are added over 2 hours, not exceeding the mixture temperature. Stir for 1 h at, poured on ice, extracted with methylene chloride. It is washed with water, dried and evaporated to dryness. The resulting residue is triturated with isopropyl ether, sucked off and dried. Obtain 21.8 g of product with so pl. 76 ° C.
    Synthesis of 2-fluoro-5-nitrobenzoic acid ethyl ester.
    Stage A. 2-Fluorobenzoic acid ethyl ester.
    35 g of 2-fluorobenzoic acid chloJ5 anhydride are introduced into 400 ml of ethanol and stirred for three hours. Allow to stand overnight. Distilled at 50 ° C / 3-4 mm Hg. Transfer to methylene chloride, washed with 5% aqueous sodium bicarbonate solution and water. The extract obtained is dried and distilled. Obtain 34 g of the desired product with t, kip. 90-91 ° C / 14 mm Hg, Art.
    Stage B. 2-Fluoro-5-nitrobenzoic acid ethyl ester.
    31.8 g of 2-fluorobenzoic acid ethyl ester are introduced into 60 ml of concentrated sulfuric acid. Stir, cool before and within 30 minutes add 15.9 g of nitric acid (density 1.5) at 0-5 C. Stir for two hours at +5 - 10 seconds. Poured into a mixture of ice and water. Extracted with methylene chloride. Combine the organic layers, wash them with a 5% aqueous solution of sodium bicarbonate and water. Dried and p-dried. Get the product, which is triturated in hexane, sucked off and dried in vacuum. Obtain 37.7 g of the desired product, m.p., 53-54 C,
    Methyl ester of 2-fluoro-5-nitrobenzoic acid.
    For 1 h, 20 g of 2-fluoro-3-nitrobenzoic acid in 60 ml of 5 ° thionyl are refluxed, the excess of thionyl is distilled off for 2 h at 25-30 ° C and left overnight. Distilled under vacuum at 50 ° C. Bring to isopropyl ether, wash, dry, and distill in vacuo. 13 g of the expected product are obtained. Mp. -52-53 ° C. 4-Nitro-4-n pentyloxy-1- -fluorobenzene is obtained by nitration of 3-fluoro-n-pentyloxybenzene, which, in turn, is produced by esterifying 3-fluorophenol (p 1.4741).
    3-Fluoro-propyloxy-benzene is prepared by the action of isopropyl iodide on 3-fluorophenol.
    1- (2-Fluoro-5-nitrophenyl) ethanol.
    2-Fluoro-5-nitroacetophenone.
    In 113 ml of nitric acid (d 1.52) at 0-10 ° C, 23.7 g-fluoroacetophenone are introduced and kept at this temperature for 30 minutes. The reaction mixture is drunk on ice, washed with water and dried. Obtain 26.98 g of the desired product with so pl. 56-58 ° C.
    1- (2-Fluoro-5-nitrophenyl) ethanol.
    To a solution of 10 g of 2-fluoro-5-nitroacetophenone in 100 ml of methanol, 1.04 g of sodium borohydride is added. The mixture is kept at this temperature for an hour, the reaction mixture is poured on ice, extracted with methylene chloride, the extract is dried, and evaporated in vacuo. 9.47 g of the expected product are obtained. 50 C.
    N B-Dieth-2-fluoro-5-nitrobenzamide.
    Chloride 2-fluoro-5-nitrobenzoic acid.
    42 g of 2-fluoro-5-nitrobenzoic acid (mp. 139 -) and 120 MP of Thionyl chloride are heated under reflux for 2 hours. The mixture is evaporated at 40 / 3-4 mm Hg. treated with benzene residue and again evaporated. Obtain 44 g of the target product, so pl. 50-60 C.
    N Y-Dietsh1-2-fluoro-5-nitrobenzamide.
    A mixture of 32 g of diethylamine and 350 mp of benzene is cooled to 5 ° C, and 40.7 g of the above acid chloride per 100 mp of benzene is added at 5-10 ° C over 30 minutes. The mixture is stirred for 1 h, filtered, the filtrate is washed with water, 1N hydrochloric acid, water, 10% aqueous bicarbonate solution, water and dried. The filtrate is treated with activated carbon, filtered again and evaporated at 50 ° C in vacuo. 38 g of product are obtained as a residue, which is chromatographed on silica gel, eluted with a mixture of methylene chloride and ethyl acetate.
    five
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    5 o

    with
    0
    tat (9: 1). Obtain 33 g of the desired product from 1.3330.
    4-Nitro-1-fluoronaphthalene (To.pl. 75 -) from 1-fluoronaphthalene.
    2-Nitro-5-fluoro-1-acetanilide (mp. 40.degree. C.) is prepared by nitration of 3-acetanylin.
    Z-Fluoro-6-nitroaniline, i
    For 30 minutes at 110-120 ° C, 20 g of 3-fluoro-6-nitroaceta- nilide are heated in 200 ml 6 n. hydrochloric acid. Pour the reaction mixture onto ice. The precipitate formed is filtered off and crystallized from isopropyl ether. Obtain 7.5 g of the desired product with so pl. 99 C.
    3-nitro-4-fluorobenzoic acid ethyl ester.
    To a solution of 10 g of 3-nitro-4-fluorobenzoic acid in 50 ml of ethanol are added 2 ml of concentrated sulfuric acid and refluxed for 3 hours. Add another 8 ml of concentrated sulfuric acid and continue to boil for 16 h. Cooled to 20 ° C and vishivaya in water with stirring. The precipitate formed is filtered, washed and dried. Obtain 10.5 g of the desired product with so pl. 50 ° C.
    3-Fluoro-allyloxybenzene (1.4985) is prepared by the action of allyl bromide on 3-fluorophenol.
    4-Nitro-3- (1-E5-hydroxyethyl) fluorobenzene is obtained by nitration of m-fluoro-acetophenone. and subsequent reduction with sodium borohydride.
    3-Fluoroethoxybenzene is obtained by the action of ethyl iodide on 3-fluorophenol (1.4823).
    3-Fluoro-n-butoxybenzene (p, 1.1580) is obtained by the action of n-butyl iodide on 3-fluorophenol (p 1.4762).
    O- (8-Nitro-5-quinolyl) hydroxyl-amine is obtained by the reaction of
    ABOUT
    ONH
    mp, 186-188 s, according to a similar scheme. Not prepared: 0- (5-nitro-6-quinolyl) hydroxyl min, mp. } (5 ° С; 0- (A- -nitro-2-isopropylphenyl) hydroxyl amine, mp. 81-82 ° C; 0- (4-fluoro-2-nitrophenyl) hydroxylamine, mp 87 i88 С ; 0- (4-nitro-3-ethylphenyl) hydroxylamine, mp 55-56 ° C.
    5-Chloro-8-nitroquinoline. : Under reflux, 25.2 g of 3-chloro-6-nitroaniliche, 21 g of mouse acid, 35.1 g of glycerol, are heated. Then, maintaining the temperature at 20–30 ° C, 25.5 ml of sulfuric acid c. Poured on ice. The precipitate formed is filtered off with suction and dissolved in methylene chloride. Neutralize the reaction medium and extract the mother liquors with methylene chloride. Combine all chloromethylene layers, dry them, treat them with activated carbon and bring to dryness. 10 g of product are obtained which is purified chromatographically on silica, eluted with methylene chloride. In this way, 8.61 g of the expected product are obtained, melting at 136-138 ° C.
    2-Nitro-4-fluorobromobenzene.
    Stage A. 2-Nitro-4-fluoroacetanide.
    13.8 g of 4-fluoroacetanilide are introduced into 35 ml of concentrated sulfuric acid. Cool down to 0 ° C and add 6.5 ml of nitric acid (density 1.42) between O and 5 ° C in 30 minutes. Stir for 2 hours at. Then, 10 MP acetic anhydride is added. Stir for 1 h at, and then poured onto a mixture of water - ice with stirring. The precipitate formed is filtered off with suction, washed and dried. This gives 14 g of the expected product (mp. 70-71 ° C).
    Stage B. 2-Nitro-4-fluoroaniline.
    40 g of 2-nitro-4-fluoroacetanilide is poured into 100 ml 8 n. hydrochloric acid solution. Stir and boil for 1 hour. Crystals are obtained. Allow to cool to 20 ° C and then oh
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    lazy. The mixture is filtered off with suction and washed with water until neutral and dried in vacuo. Receive 32.2 g of crude product (so pl. 94-95 C), which is purified by the introduction of 500 ml of methylene chloride and stirred with 300 MP 1N. caustic soda solution, decantation, washing with water, drying and distillation in vacuum. Obtain 27.2 g of the desired product with so pl. 94-95 ° C.
    Stage B. 2-Nitro-4-fluorobromobenzene.
    The suspension is stirred, containing 21.6 g of 2-nitro-4-fluoroaniline, 69 ml of 48% hydrogen bromide and 138 ml of water. Cooled to 0 ° C. 10 g of sodium nitrite is added to 30 ml of water. Stir for 10 minutes at 0 ° C. The resulting solution is introduced at 30 g of copper monobromide in 105 ml of 48% hydrogen bromide with stirring. Stir for another 1 hour at 55-60 ° C. Dilute with ice-water, extract with isopropyl ether. Combine the organic salts, dry them and distill in vacuo. The residue obtained is chromatographed on. silica, eluting with methylene chloride. The resulting product is distilled. A crystalline product is obtained which is dried under vacuum. Thus, 20.2 g of the expected product are obtained (mp. 40-41 ° C).
    Synthesis of 3-isopropyl-4-bromonitrobenzene.
    Stage A. 2-Nzopropylacetanilide.
    86 g of acetic anhydride is added to a solution of 108 g of 2-isopropylaniline in 250 ml of benzene. Stir for 16 h at 20 ° C. It is washed with water, with an aqueous solution of sodium bicarbonate and then with water. The benzene is dried and distilled off in vacuo. The residue is triturated in hexane, cooled and the resulting product is filtered off with suction. Washed with hexane and dried under vacuum. Obtain 115 g of the desired product (m.p., 67-68 C).
    Stage B. 2-Isopropyl-4-nitroacetanilide.
    A solution of 71 g of the product obtained in stage A in 300 ml of acetic anhydride and 100 ml of acetic acid is cooled to -10 ° C. Then 32 ml of nitric acid (density 1.50) are introduced for 30 minutes at 5-10 ° C. Stir for 30 minutes at -5 ° C, and then 3 hours at 0 + 2 ° C. While stirring, pour into a mixture of water and ice. The mixture is stirred for 1 h, the precipitate obtained is filtered off with suction, washed with water and dried. 70 g of the product are obtained, which is chromatographed on silica, eluting with a mixture of methylene chloride and ethyl acetate (7: 3). Thus, 19.4 g of the expected product are obtained (mp. 160-161 ° C).
    Stage B. 2-Isopropip-4-nitroaniline.
    A mixture of 19 g of 2-isopropyl-4-nitroacetanilide and 60 ml of 8 n hydrochloric acid is heated under reflux for 2 hours. The resulting solution is cooled and the precipitate formed is sucked off. It is introduced into water and alkalinized with aqueous 10% sodium carbonate solution. Extracted with isopropyl ether. Dilute with hydrochloric acid master liquids, alkalinize them, and extract with isopropyl ether. Combine the organic layers, rinse them with water, and dry. The product obtained is distilled in vacuo. Obtain 11.7 target product.
    Stage G. 3-Isoprop-4-bromonitobenzene.
    Preparation of diazonium bromide.
    A suspension of 18.5 g of 2-isopropyl-4-nitroaniline in 120 ml of a 48% aqueous solution of hydrobromic acid and 80 ml of water is cooled to -5 ° C.
    ABOUT
    7.5 grams of sodium nitrite are introduced into 20 ml of water over a period of 20 minutes. When O is stirred for 15 min and maintained at 0 ° C.
    A solution of 22 g of copper monobromide
    in 80 ml of 48% solution of methyl bromide
    People's acid is stirred and
    heated at 50-55 s. At 50-55 ° C, the solution of diazonium bromide obtained above is introduced. Stir for 1 h at 55-60 C. Cool, add water and extract with methylene chloride. Combine the organic layers, wash them with 1N sodium hydroxide solution, water, and dry. Distilled under vacuum at 50 s. Again distilled in vacuum, 20.4 g of the desired product (b.p. 150-152 ° C) 8 mm Hg are obtained.
    4-Nitro-Z-ethylfluorobenzene is obtained by nitration of 3-ethyl-fluorobenzene,
    Compounds obtained by the present method are tested as formulations.
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    Examples of the preparation of compositions.
    Emulsifiable concentrate.
    A composition is prepared containing by weight 15% of the product of Example 1, 6, 4% of Atlas 4851 (ethoxylated triglyceride combined with sulphonate, acidic, 1.5), 3.2% of Atlox 4855 (ethoxylated - glyceride combined with sulfate, acid number 3) and 75.4% xylene.
    Wettable powder.
    A wettable powder is prepared, containing 25% of the product of Example 2, 15% of ekapersol (condensation product of naphthalene sulphonate sodium), 35% of zeosil 39 (synthetic silicon dioxide, precipitated) and 25% of Verkoril (colloidal kaalin ) ..
    Study of the activity of compounds 1.
    A / Study of the effect of Warburg.
    Compounds 1 have the property of reducing the inhibitory effect of oxygen on photosynthesis (the varorgh effect), which leads to the stimulation of photosynthesis and an increase in yield.
    The tests are carried out on cut leaves of grain bread placed on the surface of distilled water, or a solution of the studied product (10 mmol per liter).
    The leaf is placed in impermeable glass chambers under 300 W / sq. m and the temperature in which 25 ° C; the chamber atmosphere is maintained by constant air blowing (21% 0g - 350 ppm COg) or pure oxygen - 100%. After reaching a constant photosynthesis rate, 0.09 µmol CO2 is introduced (specific activity: 22. micros / mM) and the leaves are left for 15 minutes under light in the presence of radioactive carbon dioxide.
    The leaves are then immersed in liquid nitrogen and stored. Next, the leaves are burned to determine the amount of COj fixed by photosynthesis. Results are expressed by fixed radioactivity ratios between control leaves and leaves treated with the test products.
    Leaves were treated with 10 micromole of the products of the following examples and placed in an atmosphere containing 100% 0g.
    The obtained results of the inhibition of the action of oxygen in relation to photosynthesis d; shy below: Example product Photosynthesis,% of
    untreated control (100) 165) 140 (MH) 138
    1 2 3 4 5
    (± 12) 145 (± 10) 125 (i-9)
    The% of photosynthesis of the leaves of grain bread, measured by CO 2 absorption in relation to the untreated control in an atmosphere containing 100% oxygen (inhibition of O2 photo synthesis in 30–50% in these studies), is shown
    B / Study of the activity of v. Quality of the growth factor products of examples 1 and
    Sample on tomatoes. The tests were carried out on Europee 1 variety tomatoes. A Fisher block was used with 5 repeats. The main plots are 20 sq. M. (10x2 m). Provides the necessary controls to each repetition. The tests are carried out on clay, lime-clay soil. The treatment is carried out using a portable device of the van der Veij type with a capacity of 750 l / ha at a constant pressure of 3 bar. The treatments are carried out either after the petals of the first flowers (T) are dropped, or after the petals of the last flowers fall (Tg T - 20 days), or during the formation of fruits (Tz Tg - 20 days).
    The products of examples 1 and 2 are applied in doses of 40, 60 or 120 g / ha in 3 doses in one. Observe two yields of tomato. At each stroke, the yield in kg per 32 saplings of tomatoes is determined relative to the untreated control (see table).
    The products of Example 2 were found to exhibit 6ojfee high activity as a growth factor than product X (a mixture of folic acid and cysteine).

    Compound
    Example 2 90 129.9 113.2
    Product X 0.5 + 30 117,3102
    Control1111.7JOO
    In the doses used, the toxicity of the compounds was not detected.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of obtaining hydroxylamine derivatives of general formula 1
    ArONHj,
    where A. g - phenyl, containing b
    1-2 nitro groups, halogen, lower alkyl or alkoxy or Ag-nitroquinolyl,
    characterized in that
    compound of general formula
    AgHal,
    where Ar has the indicated values,
    Hal - halogen,
    interact with hydroxylamine hydrochloride in an aqueous-alcoholic medium in the presence of alkali.
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    同族专利:
    公开号 | 公开日
    ES533525A0|1985-02-16|
    MA20040A1|1984-10-01|
    FR2541282A1|1984-08-24|
    EP0119892B1|1986-08-13|
    DD221456A5|1985-04-24|
    ES529940A0|1984-11-01|
    CA1219591A|1987-03-24|
    GR79524B|1984-10-30|
    DK86384A|1984-08-24|
    FR2541282B1|1985-10-11|
    PL142746B1|1987-11-30|
    KR840007870A|1984-12-11|
    HU195666B|1988-06-28|
    BR8400821A|1984-10-02|
    PL142913B1|1987-12-31|
    DK86384D0|1984-02-22|
    DE3460448D1|1986-09-18|
    AU2483684A|1984-08-30|
    RO89238A|1986-03-15|
    PL253011A1|1985-12-17|
    AU557583B2|1986-12-24|
    EP0119892A1|1984-09-26|
    OA07667A|1985-05-23|
    IL70915A|1990-07-12|
    PL246324A1|1985-08-27|
    US4801717A|1989-01-31|
    ES8503331A1|1985-02-16|
    IL70915D0|1984-05-31|
    DD258557A5|1988-07-27|
    AT21385T|1986-08-15|
    JPS59163350A|1984-09-14|
    ES8500958A1|1984-11-01|
    ZA84967B|1985-03-27|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3118933A|1959-12-28|1964-01-21|Hoffmann La Roche|N- hydroxylamine and its salts|
    FR1430927A|1963-12-20|1966-03-11|Ciba Geigy|New pesticide agents|
    FR2520194B1|1982-01-28|1984-03-16|Roussel Uclaf|CH674205A5|1988-05-11|1990-05-15|Lonza Ag|
    DE4339208A1|1993-11-17|1995-05-18|Hoechst Ag|Process for the preparation of alkyl fluorobenzoates in high purity and yield|
    AU2003261157A1|2002-07-11|2004-02-02|Scios Inc.|Improved reagents for n-amination|
    US7018851B2|2003-02-13|2006-03-28|Innotrac Diagnostics Oy|Biospecific binding reactants labeled with new luminescent lanthanide chelates and their use|
    US7214825B2|2003-10-17|2007-05-08|Honeywell International Inc.|O- hydroxylamine free base|
    JP2009544609A|2006-07-18|2009-12-17|アストラゼネカ・アクチエボラーグ|Method for producing substituted 2-acetylamino-alkoxyphenyl|
    WO2009082020A1|2007-12-21|2009-07-02|National Institute Of Advanced Industrial Science And Technology|Reactive compound having aminooxy group|
    CN109134321A|2018-10-22|2019-01-04|江苏长青农化股份有限公司|A kind of preparation method of mesotrione intermediate|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR8302916A|FR2541282B1|1983-02-23|1983-02-23|NOVEL HYDROXYLAMINE DERIVATIVES, THEIR PREPARATION PROCESS AND THEIR APPLICATION AS PLANT GROWTH FACTORS|
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