• 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 compounds of formula /1/ <IMAGE> wherein R represents a C1-12 alkyl group optionally substituted by a lower alkoxy group, a C2-4 alkenyl group or a phenyl-/lower alkyl/ group optionally substituted on the phenyl ring by one or more lower alkoxy group/s/ or halogen atom/s/, are plant growth regulants. These compounds are prepared by reacting a racemic or optically active compound of formula /II/ <IMAGE> wherein Y is an oxygen or sulfur atom or an oxime group, with a compound of the general formula /III/ R-X wherein X represents a leaving group, preferably a halogen atom, a sulfonyloxy or an aminooxy group, with the proviso that when using a compound of the general formula /II/, in which Y is an oxime group, X is other than aminooxy group, in the presence of a basic condensing agent, and optionally resolving the racemic compound of the general formula /I/ obtained into its optically active antipodes.
    公开号:SU1209027A3
    申请号:SU813369302
    申请日:1981-11-20
    公开日:1986-01-30
    发明作者:Будаи Золтан；Киш Тамаш Аттила；Мезеи Тибор；Лай Аранка；Вигх Золтан；Шокораи Агнеш
    申请人:Эдьт Дьедьсерведьесети Дьяр (Инопредприятие)；
    IPC主号:
    专利说明:

    The invention relates to the methods of obtaining: and new bicyclic derivatives of - (2.2) 1 heptane of formula T regulating the growth of plants, namely k; -1O7, racemic or optically active compounds of the general formula;
    Luch
    one
    SI
    he
    where k is an alkyl group with 1-} 2
    atomash1: a carbon Cj alkenyl group or a fe — Htui- (lower apkyl) group. substituted in the phenyl ring in the corresponding single halogen atom, These compounds are
    plant growth stimulus,
    II p and m er 1 Preparation of (± - 2- (al.tgloxirshino -1.7, U-trimethyl-β-cloc (. 2 g 2 5 I) -entanao
    4.6 g (052 g-atom) metal; sodium hydroxide is dissolved in 20 methanol, after which 33.4 g (05.2 mol) of (+) -oxime 2 -1,7,7 is added to the solution -trimethyl-bicyclo- (2,2,1) -entan-2-one. The mixture is heated to boiling for 2 hours. After adding 24.0 g (0,, 2 mol) of the al1-t-bromide, the reaction mixture is heated to boiling for another 3 hours. The resulting suspension is cooled, the sodium bromide precipitated is filtered, the filtrate is evaporated and subjected to fractionation under reduced pressure. 31.2 g of the expected product are obtained. Yield 77%. Colorless oil boils at 92 ° C at 200 mm Hg. Rp 1.4882.
    Example 2: Preparation of (-) - 2-allyloxyimino, 7,7-trimethyl-bicyclo- (2.2.1) ngpc.
    To 150 ml of anhydrous benzene, g (mol) of sodium hydride is added. A solution of 33.4 g (0.2 mol) of (+) - 5 7 ,, 7-trimethyl-bi-iiklo (2, 2,1) -heptan-2-one ox1-1ma n 60 ml of anhydrous dimethyl forms is added - yes within half an hour at 50 ° C. At the end of the gas, the mixture is cooled to 25 ° C. After adding 15.3 g (0.2 mol) of allylchloride, and the reaction mixture is heated to boiling for 2 hours, then washed 1209027 2
    WATER, The benzene phase is evaporated and the residue is subjected to vacuum distillation. 34., 4 g of the expected compound are obtained. Yield 85%. The
    5 boiling point 92-94 ° C at
    200 km of mercury, st, p 1.4870, (ti) i ° -25 48 48 (methanol),
    PRI me R 3. Obtaining (+) .- (il-propyloxyimino) -1 5 7, 7-three 0 methyl-bicyclo-(2,2,1) -heptane. To 800 ml xylene, add g (1.0 mol of finely ground sodium sulfide 5, after which a solution of 167.0 g is added at 50 ° C.
    15 (1 5O mol) (±) -1, 7,7-trimethyl-bi-iiklo (2 5.2 51) teptan-2-one oxime and 200 ml of dimethylformamide. At the end of the evolution of gas at 50 ° C, 123.0 g {1.0 mol) of p-pro20 pilbromide is added, the reaction mixture is stirred for 1 {2 hours at
    WITH
     C, The resulting suspension at 20 ° C is washed several times with water. Content of effective substance
    25 E. The x-phase phase is determined by gas chromatography. Yield 782 g (in the form of a xylote solution containing 25.6% of the effective Eescot-95% j,
    30 The reaction mixture can be formed in such a way as to evaporate the xylene solution under reduced pressure, and the residue is subjected to vacuum distillation.
    j, j Get 192.6 of the title compound as a colorless oil. Yield 92%, Boiling point 90 ° C at 250 mm Hg, 11. p.
    PRI me R 4. Obtaining (-) - 24U .. (allyloxyimino) - i 57,7-Trimetnl- -bi: hiclo (2 j 2 5 1) -heptane
    To a solution of 76.0 g (0.5 mol (-f) -1., 7, 7-trimethyl bicyclo - (2.2, I) - -111 - 2, 225: lp of pyridine and
    i 500 ml of anhydrous ethanol was added 60 g (0.55 mol) of altyloxime hydrochloride. The reaction mixture is heated to boiling for 3 hours and the nocj i. E. Is evaporated under reduced pressure. 50 ml of water are added to the residue. The product is extracted, their. LQ pretanom. the organic phase is xpar and the residue is subjected to vacuum distillation. The target compound, Kenya, is obtained in the form of a colorless powder in the amount of 85.0 g.
    Output 81.5%. Boiling point 92-95 ° C at 200 mm Hg.
      l, 4868. ("6) -25.52 ° (, methanol).
    P p and m e p 5. Preparation of (±) -2- - (allyloxyimino) -, 7,7-trimetnl- -bicyclo- (2,2,1) -heptane.
    The method is carried out as described in Example 9 with the difference that as the starting compound
    . 76.0 g (0.5 mol) (±) -1.7, 7-trimethyl-bicyclo (2.2.1}) - heptane-2-thione are used. 83.5 g of the expected compound are obtained. The output of 80.6%. Boiling point: 94-96 ° C at 250 mmHg, p = 1.4884. . Example 6. Obtaining (-) - 2, - (n-propyloxyimino) -1,7,7-trimethyl-bicyclo- (2,2, 1 -heptane.
    40.0 g (1.0 mol) of powdered sodium hydroxide and 50 ml of methanol are added to 800 ml of xylene, after which the suspension is heated to boiling for 30 minutes and then cooled to 30 ° C. After adding 167.0 g (1, 0 mol) oxyma (+) -, 7,7-trimethyl-bicyclo (2.2, -heptan-2-it) the reaction mass is slowly heated to boiling. Methanol and water formed in the reaction (18.0 ml, 1 , 0 mol) is distilled using a Markusson nozzle. The suspension is cooled to -30 ° C. 200 ml of anhydrous dimethylforma 1id and 123.0 g (1.0 mol) of p-propyl bromide are added. The reaction mixture is stirred for 2 hours at 85-90 ° C, repeatedly washed with water and the xylene solution is dried over anhydrous magnesium sulphate. The content of the effective substance is determined by gas chromatography. The content of the effective substance is 24.5% yield 818.5 g (95.8% ).
    The reaction mixture can also be processed as follows.
    The xylene solution under reduced pressure is evaporated and the residue is subjected to vacuum distillation. Yield 190.9 g (91.2. Boiling point 85-87 ° С at 200 mm Hg (6) ° -22.48 (, ethanol).
    Example 7: Preparation, (+) - 2- - (benzyloxyimino) -1,7,7-trimethyl-bicyclo- (2.2, 1) -heptane.
    The method is carried out analogously to example 6 with the difference that instead of P-PRopil bromide, 126.5 g (1.0 mol) of benzyl chloride are used. 201.3 g of the expected compound are obtained.
    09027Л
    The yield is 78.3%. The boiling point is 31 ° C at 80 mmHg 1.5250.
    Example 8, Preparation of (+) - (to dedecyloxyimino) -, 7, 7-trimet1-sh-bi-5 cyclo- (2,2,1) -heptane.
    The method is carried out in a manner similar to that of p-iepy 6 with the difference that instead of p-prop-bromide, 249.2 g (1.0 mol) of dodecyl bromide is used. .10 Get 273.1 of the title compound. Yield 81.4%. Boiling point at 40 mm Hg. P 1,4685. Example 9. Preparation of (+) - 2- - (4-Chlorobenzyloxyimino) -1,7,7-tri-15 methylbicyclo- (2.2.1) -heptane.
    The method is carried out analogously to Example 5 with the difference that, instead of propyl bromide, 161.0 g (1.0 mol) of 4-chloro-20 benzyl chloride are used for the reaction. Yield 241.8 g (83.1%). Boiling point: 166 C at a pressure of 105 Pa. ti 1,5380
    Example 10. Preparation of (±) -2- - / allyloxyimino-, 7,7-trimethyl-25 bicyclo- (2.2, l-heptane.
    150 ml of anhydrous benzene are mixed with 4.8 g (0.2 mol) of sodium hydride and 50 ml of dimethylformamide, after which a solution of 33.4 g (0.2 mol (+)) is added to the prepared mixture 30 at 15 ° C. 7,7-trimethylbicyclo- (2,2,1) - -heptan-2-one-oxime with 50 ml of anhydrous dimethylformamide. Upon completion of gaseous emission
    at 15 ° C, 24.0 g (0.2 mol) of allyl bromide was added to the mixture while cooling vigorously so that the temperature of the reaction mixture remained at the level of 15 ° C. After stirring for 6 hours, the reaction mixture is washed with water, the benzene phase is evaporated and the resulting residue is subjected to a D5 fractional distillation in vacuo.
    Yield 33.6 g (83%), colorless oily substance. Boiling point 92 C at 200 Pa. ni 1,4880.
    The compounds obtained according to the proposed method can be used for regulating the growth of plants at the stage of development of the first 55 and second germinal leaves. The treatment can take place before sowing, before vyivanieI, before germination, and.ta-i after germination.
    S
    Processing can be carried out by introducing into the ground.
    By treatment before sowing or before planting, it should be understood that the medium obtained according to the proposed method is introduced into the ground and the seeds or plants are sown and planted only immediately after this,
    The treatment before germination means that these compounds are applied to the ground before germination, for example, the ground is sprayed with a means when the germinal plants are not yet on the surface of the earth.
    By treatment after germination, it should be understood that the compounds obtained in accordance with the invention, after germination of plants, are applied to the area to be treated, for example, the plant or ground parts are treated separately.
    It has been determined that the compounds produced according to the invention particularly affect such cultivated plants as maize, cereals, sunflower, alfalfa, sugar beets, rapeseed, co, potatoes, rice, pepper-paprika, tomatoes, and ravines.
    The amount of effective substance required by the invention for beneficial effect depends on many factors; For example, from the optical configuration of an effective compound (racemate, left or right, the type of crop that can be processed, etc., Therefore, the optimal dose in each case should be determined fflichicheski, ka.a., per hectare apply 0.1-- 25 kg preferably 0.1-15 kg of effective substance
    The biological effect of compounds of the general formula D can be as high as
    using the tests below.
    1 "Greenhouse experience. A plastic container with a surface of 168 cm is filled with washed river sand. Grains of the tested plants are sown in the sand. As such, corn, sunflower, pea, barley, rape and 10 tomatoes are used. 10 --- 12 grains are sown in each tank. Before germination, the broth is sprayed for spraying simultaneously with seeding. After germination, treatment 15 is carried out at the stage of development of 2-3 leaves.
    Processing was carried out four times. The plants are kept at an average temperature of 18-24 05 natural light and in greenhouse conditions.
    When estimating, the weight of green mass of untreated control samples is taken as 00% and the average values of individual treatments refer to
    25
    corresponding value of control samples In another estimate, the average weight of plants at the stage of development of a single germ sheet and two germinal leaves refers to 30 to the average weight of untreated control samples.
    The following test compounds were used;
    A. (+) - 2- (dodecyloxyimino) - 35 7-trimethyl-bicyclo (2,2,1) -heptane.
    B- (+) -2 - (| 1-propoxyimino) - (1.7, 7-trimethyl-bicyclo (2.2.1) -heptane.
    C. (-) - 2 - (Allyloxyimino) - (1, 7, 40 7-trimethyl-bicyclo (2.2.1) -heptane.
    I, (+) - 2 (allyloxyimino) -1,7,7-trimethyl-bicyclo (2,2,1) -heptane.
    S. (+) - 2 (2- (4-chlorobenzyloxy-imino) -15 7,7-trimethyl-bicyclo- (2.2.1) - 45-heptane.
    The results are shown in Table. one.
    From the compound A of Example 1, at once, an emulsifiable concentrate is obtained by spraying broth to produce corn, sunflower, (50 EC), which upon dilution of peas.
    water is transferred to the broth for spraying. Results of the presentation. Cooked in this way are in Table 2.
    table 2
    Emulsifiable concentrate, half-processed corn, peas, volume. Combined from compound B dilution.
     water, translate into broth for
    spraying. The resulting broth 50 in the table. 3
     Table3
    Treatment
    Corn
    0.5 kg / ha | 2 | sg / ha | 5kg / ha p, 5kg / ha 2kg / ha 5 kg / ha | o, 5kg / ha 2kg / ha | 5kg / ha
    Green mass,%
    | 1 before germination 140 140 Doslv germination PO 112
    120 140 108 230
    Table. one
    Peas
    Tomatoes
    90 200
    95 98
    120 92
    102 99
    The emulsifiable concentrate obtained from compound C is diluted with water into broth for spraying.
    Treatment
    Corn
    t a b and ToHBfH podsolnachink | Peas
    0.5 kg / haKg / gfkg / ha OsSitr / ra 2kg / {arkg / gf, 5k1- / harkg / ha | 5kg / ha, 5kg / ha 2kg / g,
    Green mass, Z
    Before germination
    After germination 135
    I20 190 100 100
    100 SOO 20 155 155 180 100 100 00 95 100 10U PO 35 200 100 100 100
    The emulsified 1 ", 1st concentrate, obtained from compound f by dilution with water, is transferred into broth. spraying.
    Before germination .PO 115 115 220 180 20
    After germination 96 103 100 160 155 125
    2. Greenhouse experience.
    The test was carried out under greenhouse conditions at a neutral pH of the earth. Test compounds are applied to the surface of the seeds as a coating film. The size of the treated surface capacity i 5 3060 cm, the number of repeat control
    A50
    B50
    CIO
    The results of the tests were carried out with the broth thus obtained for spraying. On corn, sunflower, peas and tomatoes are given in Table. four.
    t a b and c a 4 ToHBfHkg / ha
    kg / ha 2kg / g,
    The results of experiments carried out with this broth for: sprinkling-) 1i on corn and peas are given in Table 5;
    T a b l and c a 5
    35 SRI 45 average temperature 18–24 ° C. The average results of repeated experiments refer to the average results obtained on untreated samples (control). 40 The test plant is corn (variety SZSC- -jUU).
    The results are shown in Table 6. Table 6
    3. Greenhouse experience.
    The experiment was carried out analogously to Example B, with the difference that the effective substance was not applied as a seed coat, but as a microgranule before germination into the ground with an effective substance content of 10%. The treatment after germination is carried out by spraying broth obtained with one of the emulsifiable concentrates, for example, 1J.
    HcinbijyeMoe plant - maize (variety KSC-Zbo). The average temperature is 24 ° C.
    Obtained by processing before germination results are shown in Table. 7. The height of the plants on the 21st day after germination was determined to be in the% control samples.
    Table 7
    1 Continuation of table 6
    The results obtained during treatment after germination are shown in Table. 8. Cultivated corn in the development stage of 3-5 leaves.
    Table B
    . From the above tables it is clear that compounds of the general formula 7 have a stimulating effect on plant growth and height, as in the case of treatment before germination, and E
    5Q case treatment after germination. Particularly favorable results are obtained when processing before germination.
    The effect on the weight of the green mass and on the dry weight proves the results given in Table 9 (treatment before germination).
    13
    control
    ABOUT
    4 8 2 4 8 2 4
    77 P4
    96.5
    102 129
    122 108 1 13
    45
    In tab. 10 shows comparative data with lime derivatives of bicyclo- (252.1) -heptane,
    T a b l and c a 10
    Connection by PRIVNIIPI Order 308/61 TirshO79 Subscription Branch PPP Patent, city street, Project 4 Yadgorod St.
    .20902714
    T a b l and c a 9

    ten
    10.5 9.3 8.7
    10, i
    10.4
    9.1
    6.8
    10.8
    10.6
    100 129 134 119 1 1 1 129 1 10 133 116 87 138 135
    Out of 50 EC-forms of the compound according to nrotrotine, as well as according to Example 8, but the invention is prepared with a load of 500 liters of water broth for spraying. The resulting broth was applied by spraying before flowering on the leaves in a tomato culture,
    The preparation according to the prototype at a dose of 1 kg / ha. Is not phytotoxic at a dose of 5 kg / ha, however, at a dose of 10 kg / ha, strong phytotoxicity is observed.
    The compound according to Example 3, at doses of 1 and 5 kg / ha, is non-phytotoxic. At a dose of 10 kg / ha, cJieppia plants will rise and only at a dose of 20 kg / ha is observed Siotn phytotoxicity. From this it follows that cultured plants are also tolerant to higher doses. New derivatives of bidicles (2.25l) -heptane.
    权利要求:
    Claims (3)
    [1]
    1. A method of obtaining derivatives of bicyclo- (2,2,1) -heptane of the general formula G where R is C ( _ | g- alkyl, C ^ -alkenyl or, if appropriate, phenyl- (lower alkyl) substituted in the phenyl ring by one halogen atom ) -group, or its optically active antipode, characterized in that, racemate or optically active compound of the formula II where Y is oxygen, sulfur or an oxime group,
    - in the presence of a basic condensing agent and an organic solvent at a temperature from room temperature to the boiling point of the reaction mixture, it is reacted with a compound of formula III g
    RX, where R has the indicated meaning;
    X is halogen, an oxime group, provided that when using a compound of formula II where Y is an oxime group, X is different from the oxime group and the target product is isolated as a racemate or an optically active antipode.
    [2]
    2. The method according to claim 1, characterized in that, as the main condensing means, alkali metal hydroxide, alkali metal hydrides, alkali metal amides, alkali metals or organic bases are used.
    [3]
    3. The method according to π. I, characterized in that benzene, xylene, dimethylformamide, methanol, ethanol are used as an organic solvent.
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    引用文献:
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    GB2031874B|1978-08-22|1982-12-15|Egyt Gyogyszervegyeszeti Gyar|Plant growth regulating and insecticidal compositions|
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    HU184353B|1980-11-21|1984-08-28|Egyt Gyogyszervegyeszeti Gyar|Plant growth regulating composition containing bicyclo/2.2.1/ heptane derivative further process for preparing bicyclo/2.2.1/ heptane derivatives|HU184353B|1980-11-21|1984-08-28|Egyt Gyogyszervegyeszeti Gyar|Plant growth regulating composition containing bicyclo/2.2.1/ heptane derivative further process for preparing bicyclo/2.2.1/ heptane derivatives|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    HU802774A|HU184353B|1980-11-21|1980-11-21|Plant growth regulating composition containing bicyclo/2.2.1/ heptane derivative further process for preparing bicyclo/2.2.1/ heptane derivatives|
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