Use of a composition and a method for the promotion of plant production and/or for the elimination of the unfavorable influences in plant cultivation

Compositions containing hydroximic acid derivatives of the formula ##STR1## where R.sup.1, R.sup.2, R.sup.3, R, X, Y, A, and B are as defined in the specification, are useful for the promotion of plant production and/or for the elimination of unfavourable environmental influences in plant cultivation.

The invention refers to the use of a composition and a method for the
 promotion of plant production and/or for the elimination of the
 unfavourable environmental influences in plant cultivation.
 More specifically, the invention refers to the use of a composition
 comprising a hydroximic acid derivative of the formula
 ##STR2##
 wherein
 R.sup.1 represents a hydrogen atom or a C.sub.1-5 alkyl group,
 R.sup.2 stands for a hydrogen atom, a C.sub.1-5 alkyl group, a C.sub.3-8
 cycloalkyl group or a phenyl group optionally substituted by a hydroxy or
 a phenyl group, or
 R.sup.1 and R.sup.2 together with the nitrogen atom they are attached to
 form a 5 to 8 membered ring optionally containing on or more further
 nitrogen, oxygen or sulfur atom(s) and said ring can be condensed with
 another alicyclic or heterocyclic ring, preferably a benzene, naphthalene,
 quinoline, isoquinoline, pyridine or pyrazoline ring, furthermore, if
 desired and chemically possible, the nitrogen and/or sulfur heteroatom(s)
 are present in the form of an oxide or dioxide,
 R.sup.3 means a hydrogen atom, a phenyl group, a naphthyl group or a
 pyridyl group wherein said groups can be substituted by one or more halo
 atom(s) or C.sub.1-4 alkoxy group(s),
 Y is a hydrogen atom, a hydroxy group, a C.sub.1-24 alkoxy group optionally
 substituted by an amino group, a C.sub.2-24 polyalkenyloxy group
 containing 1 to 6 double bond(s), a C.sub.1-25 alkanoyl group, a C.sub.3-9
 alkenoyl group or a group of the formula R.sup.7 --COO-- wherein R.sup.7
 represents a C.sub.2-30 polyalkenyl group containing 1 to 6 double
 bond(s),
 X stands for a halo atom, an amino group, a C.sub.1-4 alkoxy group, or
 X forms with B an oxygen atom, or
 X and Y together withv the carbon atoms they are attached to and the
 --NR--O--CH.sub.2 -- group being between said carbon atoms form a ring of
 the formula
 ##STR3##
 wherein
 z represents an oxygen atom or a nitrogen atom,
 R stands for a hydrogen atom or
 R forms with B a chemical bond,
 A is a C.sub.1-4 alkylene group or a chemical bond or a group of the
 formula
 ##STR4##
 wherein
 R.sup.4 represents a hydrogen atom, a C.sub.1-5 alkyl group, a C.sub.3-8
 cycloalkyl group or a phenyl group optionally substituted by a halo atom,
 a C.sub.1-4 alkoxy group or a C.sub.1-5 alkyl group,
 R.sup.5 stands for a hydrogen atom, a C.sub.1-4 alkyl group or a phenyl
 group,
 m has a value of 0, 1 or 2
 n has a value of 0, 1 or 2,
 with the proviso that Y is other than hydroxy when X is an amino group,
 or a physiologically acceptable acid addition salt thereof as the active
 ingredient.
 The hydroximic acid derivatives of the formula I are known.
 U.S. Pat. No. 4,308,399 describes hydroximic acid derivatives within the
 compounds of the formula I suitable for the treatment of diabetic
 angiopathy.
 EP No. 417 210 also describes hydroximic acid halides within the formula I
 having a selective beta-blocking effect, thus, being suitable for the
 treatment of diabetic angiopathy.
 HU-P Application No. 2385/92 published under No. T/66350 describes further
 hydroximic acid derivatives within the formula I. These known compounds
 can be used in the treatment of vascular deformations, mainly in the
 therapy of diabetes mellitus.
 Plants have a very important role from the point of view of the life on the
 earth. They are nutrient source for the animal world including man, and
 they have a considerable part in the preparation of oxygen that is
 essential for the life.
 For the optimal growth and production conditions of plants they have to be
 adaptable to the environmental conditions. If these environmental factors
 are suddenly changed in a drastic manner (e.g. due to a long-lasting
 drought, a sudden cooling down to about 0.degree. C. or the appearance of
 acidic, mutagenic or radiating agents in the environment), then the
 fertility and in many cases even the surviving ability of plants are
 significantly reduced.
 The plants are especially sensitive to these sudden unfavourable changes in
 the germinating state since their natural defensive ability i.e. a certain
 buffering ability have not developed yet to a sufficient extent.
 Thus, there is a need to find substances having low or high molecular
 weight which could enhance the natural defensive mechanisms of plants to
 increase the survival chances thereof in case of extreme environmental
 changes.
 Presumably, such substances should have general properties that promote the
 maintenance or regeneration of the biological integrity of plant cell
 membranes. Furthermore, such substances should be able to induce the
 defensive mechanisms of plant cells, thus, avoiding the irreversible
 damage of the chromosome set or the mitochondrial genom of the cell.
 Owing to substances having the above properties plants could probably
 tolerate the detrimental effects of chemical or mutagenic agents that
 appear in the environment.
 If, by means of such substances, plants are able to tolerate the low water
 concentration of the cells for a longer time, then also lands having a
 restricted water supply could be cultivated.
 If the germinating seeds could be made resistant to low temperature or they
 could tolerate cooling down to a temperature below freezing point for a
 limited time, then certain domesticated plants could be sowed sooner, on
 the one part, and the crop land there of could be shifted to northern
 areas, on the other. In both cases a considerable economical benefit can
 be expected.
 It was found that the above need is fulfilled by the use of a composition
 of the invention comprising a hydroximic acid derivative of the formula I
 or a physiologically acceptable acid addition salt thereof as the active
 ingredient.
 Thus, the composition used according to the invention comprises a
 hydroximic acid derivative of the formula I or a physiologically
 acceptable acid addition salt thereof as the active ingredient in
 admixture with one or more conventional solid or liquid carrier(s) of
 compositions used in plant protection.
 In the specification and claims a C.sub.1-5 alkyl group is, for example, a
 methyl, ethyl, n-propyl, isopropyl, n-butyl or n-pentyl group, peferably a
 methyl or an ethyl group.
 A C.sub.3-8 cycloalkyl. group is, for example, a cyclopropyl, cyclopentyl,
 cyclohexyl, cycloheptyl or cyclooctyl group, preferably a cyclopentyl or a
 cyclohexyl group.
 A 5 to 8 membered ring containing one or more heteroatom(s) can be, for
 example, a pyrrole, pyrazole, imidazole, oxazole, thiazole, pyridine,
 pyridazine, pyrirmidine, piperazine, morpholine, indole, quinoline etc.
 ring.
 A C.sub.1-24 alkoxy group is, for example, a methoxy, ethoxy, n-propoxy,
 tert.-butoxy, n-pentoxy, decyloxy, dodecyloxy, octadecyloxy etc. group.
 A C.sub.1-25 alkanoyl group is, for example, a formyl, acetyl, propionyl,
 butiryl, caproyl, palmityl, stearyl etc. group.
 A C.sub.3-9 alkenoyl group is, for example, an acryloyl, pentenoyl,
 hexenoyl, heptenoyl, octenoyl etc. group.
 A C.sub.1-4 alkylene group is, for example, a methylene, ethylene,
 propylene or butylene group.
 A halo atom is, for example, a fluoro, chloro, bromo or iodo atom,
 preferably a chloro or a bromo atom.
 If Y stands for a group of the formula R.sup.7 --COO--, it can represent,
 for example, a linolenoyl, linoloyl, docosahexanoyl, eicosapentanoyl,
 arachidonoyl etc. group.
 The physiologically acceptable acid addition salts of the compounds of the
 formula I are the acid addition salts formed with physiologically
 acceptable inorganic acids such as hydrochloric acid, sulfuric acid etc.
 or with physiologically acceptable organic acids such as acetic acid,
 fumaric acid, lactic acid etc.
 A preferred subgroup of the compounds of the formula I consists of the
 hydroximic acid derivatives of the formula
 ##STR5##
 wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, m and n are as stated
 in relation to formula I, X represents a halo atom or an amino group, Y
 means a hydroxy group,
 with the proviso that Y is other than hydroxy when X is an amino group.
 Especially preferred compounds of the formula II are those wherein R.sup.1
 and R.sup.2 together wiih the nitrogen atom they are attached to form a
 piperidino group, R.sup.3 stands for a pyridyl group, m and n have a value
 of 0, X is as defined above. Of these compounds, preferred species are as
 follows:
 N-/2-hydroxy-3-(peperidinyl)propoxy/-3-pyridinecarboximidoyl chloride.
 A further preferred subgroup of the hydroximic acid derivatives of the
 formula I consists of the compounds of the formula
 ##STR6##
 wherein R.sup.1, R.sup.2, R.sup.3 and A are as stated in relation to
 formula I.
 Another preferred subgroup of the hydroximid acid derivatives of the
 formula I consists of the compound of the formula
 ##STR7##
 wherein R.sup.1, R.sup.2, R.sup.3 and A are as stated in relation to
 formula I, Z represents an oxygen or a nitrogen atom.
 A still further preferred subgroup of the hydroximic acid derivatives of
 the formula I consists of the compounds of the formula
 ##STR8##
 wherein R.sup.1, R.sup.2, R.sup.3 and A are as stated in relation to
 formula I, R.sup.6 stands for a C.sub.1-4 alkyl group.
 The compounds of the formula I can be prepared by the processes known from
 HU-P Nos. 177 578 and 207 988 as well as from HU-P Application published
 under No. T/66350.
 The composition used according to the invention contains 0.01 to 95% by
 weight, preferably 0.1 to 20% by weight of a hydroximic acid derivative of
 the formula I or a physiologically acceptable acid addition salt thereof
 as the active ingredient in admixture with one or more conventional solid
 or liquid carrier(s) of compositions used in plant protection.
 The composition used according to the invention can be solid or liquid,
 thus a powder mixture, solution, suspension, emulsion etc.
 Essentially, any type of the compositions employed in plant protection may
 contain the active ingredient of the formula I.
 Correspondingly, the carrier can be a solvent such as water, ethylene
 glycol, propylene glycol, glycerol, poly(ethylene glycol), vegetable oil,
 mineral oil etc.; a surface active agent such as an ionic or nonionic
 emulgator; a conventional agent used in cultivation for amelioriation work
 such as powdered limestone, powdered dolomite, perlite grist, fertilizer,
 mineral salt, microelement, plant protective agent such as fungicide etc.
 Suitably, the composition used according to the invention is diluted with
 water before use, and in general the solution, suspension or emulsion
 containing 0.0001 to 1.0% by weight of the compound of the formula I is
 employed for the treatment or leaf or root thereof is contacted with the
 compound of the formula I or a physiologically acceptable acid addition
 salt thereof and a solution, suspension or emulsion containing said
 compound, respectively.
 For example, the seed of the plant to be cultivated can be treated with a
 seed-dressing composition comprising a compound of the formula I, or a
 seedling of the plant can be sprayed with a solution, suspension or
 emulsion comprising a compound of the formula I.
 The plant cultivated or the leaves thereof can be contacted through
 spraying with a solution, suspension or emulsion of a compound of the
 formula I, or the soil around the roots can be sprinkled with said
 solution, suspension or emulsion.
 A further possibility of treatment consists of adding a concentrated or
 diluted form of the composition of the invention to the spray used during
 the conventional plant protection work to obtain a final spray containing
 the compound of the formula I in the required concentration. In this way,.
 the treatment of the invention is performed together with the conventional
 plant protection treatment.
 Thus, a further embodiment of the invention consists of a method for the
 promotion of plant production and/or for the elimination of the
 unfavourable environmental influences in plant cultivation. According to
 the method of the invention, the plant to be cultivated or a seed or
 seedling or leaf or root thereof is treated with an effective non-toxic
 amount of a hydroximic acid derivative of the formula I or a
 physiologically acceptable acid addition salt thereof.
 Preferably, the plant to be cultivated or a seed or seedling or leaf or
 root thereof is treated with a composition comprising 0.0001 to 1.0% by
 weight of a compound of the formula I or a physiologically acceptable acid
 addition salt thereof in admixture with one or more conventional solid or
 liquid carrier(s) of compositions used in plant protection.
 Under the term "unfavourable environmental influences" for example nutrient
 deficiency, stress, the presence of heavy metal salts in the soil, and/or
 too cold or too warm environment etc. are meant. If seeds treated with a
 compound of the formula I are used for the cultivation, the plants are
 treated once or several times with a solution, suspension or emulsion of a
 compound of the formula I, the growth of the plants resist to the
 unfavourable environmental influences.
 The compositon and method of the invention can be preferably used in the
 cultivation of plants such as maize, bean, muscat melon, sunflower,
 tomato, capsicum, white mustard, poppy, amaranth, pigeon-berry, apricot,
 peach etc.
 The effect of the compounds of the formula I on the plant cultivation was
 studied as given below:
 In the experiments the following active ingredient was used: compound "A":
 N-/2-hydroxy-3-(piperidinyl)propoxy/-3-pyridinecarboximidoyl chloride
 malate.
 1. Study of Frost Resistance on Maize
 For the investigation of the frost resistance, the surface of the maize
 seeeds was treated with the aqueous solutions of the active ingredients.
 The concentration of the solutions used were: 1 g/l; 0.1 g/l; 0.01 g/l;
 and 0.001 g/l. After the treatment the seeds were placed onto a filter
 paper and let to germinate by adding the required amount of water at a
 uniform ratio. Then the seeds, germinated or not, were implanted into
 normal mould placed in plastic flacons. 20 ml of tap water were added to
 each flacon day by day. 14 to 15 days after the treatment of the seeds the
 plastic flacons were placed into a freezer (Zanussi, 50 litres) and left
 there for the indicated time at -17.degree. C. Then the flacons were
 removed, the freezer was left to cool down to -17.degree. C., and further
 plastic flacons were placed into it taking care that always the same mass
 of flacons should be placed in.
 The number of experiments that could be performed was highly restricted by
 the fact that the natural Yearly biorythm of the plants must be followed.
 In case of a deviation from the biorythm exceeding a month, the results
 obtained cannot be compared with plants grown on free land.
 The germination ratio of maize seeds was equivalent to nearly 100%, thus it
 is not indicated in detail.
 1.1 Frost Treatment in Function of Time
 To study the effect of compound "A" always 50 pieces of maize seeds were
 treated with a solution thereof having the same concentration. Then the
 seeds were divided into groups consisting of 10 to 11 pieces. One group of
 the germinated and implanted seeds were subjected to frost treatment for
 10 minutes, another group of the germinated and implanted seeds were
 subjected to frost treatment for 15 minutes and a further group of the
 germinated and implanted seeds were subjected to frost treatment for 20
 minutes. The ratio (in percentage) of the surviving plants is given in
 Table I in case of the treatment with a 0.01 g/l solution of compound "A".
 In the control group the maize seeds were treated with water.
 TABLE I
 Seed Number of seeds
 group treated damaged Survival in %
 Treatment at -17.degree. C. for 10 minutes
 control 11 9 18.18
 test 10 4 60.00
 Treatment at -17.degree. C. for 15 minutes
 control 10 7 30.00
 test 11 1 90.91
 Treatment at -17.degree. C. for 20 minutes
 control 10 8 20.00
 test 10 1 90.00
 From Table I it can be seen that compound "A" can protect the plant at a
 concentration of 0.01 g/l from freezing even in a frost treatment lasting
 for 20 minutes. The effective dose for a seed amaounts to 0.182 mcg.
 1.2 Survival of Maize after a 10 Minutes' Frost Treatment
 The maize plants having 3 to 4 leaves grown from the seeds treated with the
 aqueous solutions of compound "A" were subjected to the frost treatment at
 -17.degree. C. for 10 minutes. The study simulated the physiological state
 when maize plants were endangered by early frosts in April. The results of
 the survival tests are summarized in Table II.
 TABLE II
 Conc. of
 compound Number of plants
 "A" in g/l unharmed damaged total Survival in %
 1.0 24 5 29 82.70
 0.1 22 7 29 75.80
 0.01 20 7 27 74.10
 0.001 22 5 27 81.50
 From Table II it can be seen that an excellent frost resistance is obtained
 in case of a treatment with compound "A" even at a solution concentration
 of 0.001 g/l.
 2. Study of the Promotion of Plant Growth
 The maize plants obtained from the seeds treated with aqueous solutions of
 compound "A" of different concentrations were grown and the height of each
 plant as well as the average height was determined on day 11 and 14,
 respectively. The control group was treated with water. The results
 obtained are shown in Tables III and IV,
 TABLE III
 Height of maize treated with compound "A" after 11 days
 Height (in cm) of plants treated
 with compound "A" in g/l solution
 1.0 0.1 0.01 0.001 Control
 26 62 56 140 1
 64 23 30 119 3
 46 73 50 105 2
 109 22 54 76 1
 62 64 22 76 3
 50 60 40 80 4
 40 61 36 107 2
 79 82 10 33 1
 61 31 22 114 1
 58 34 77 166 3
 66 41 40 30 3
 58 88 56 53 1
 52 67 88 39 3
 42 67 66 42 2
 75 54 40 15 1
 48 67 27 42 1
 42 29 33 9 1
 33 33 43 76 3
 69 42 18 36 1
 67 40 58 17 1
 56 58 54 72 2
 54 28 52 43 2
 65 12 -- 47 1
 30 63 -- 67 2
 33 57 -- 82 2
 10 50 -- 16 1
 -- -- -- 11 2
 -- -- -- -- 1
 -- -- -- -- 1
 Number of plants 26 26 22 27 29
 Average height 53.7 50.3 44.2 63.4 1.8
 TABLE IV
 Height of maize treated with compound "A" after 14 days
 Height (in cm) of plants treated
 with compound "A" in g/l solution
 1.0 0.1 0.01 0.001 Control
 147 110 156 140 45
 172 130 72 119 12
 190 28 85 105 18
 75 78 155 76 22
 109 109 153 76 37
 77 101 18 80 16
 47 63 28 107 29
 108 146 64 33 24
 84 152 90 114 35
 74 156 93 166 16
 109 54 69 30 49
 142 159 34 53 18
 8 175 50 39 23
 6 97 83 42 36
 18 111 106 15 25
 160 145 85 42 14
 221 163 135 9 38
 97 70 141 76 43
 129 146 111 36 11
 75 38 176 17 39
 125 108 173 72 28
 102 24 120 43 12
 187 139 168 47 44
 141 168 101 67 53
 155 153 43 82 17
 150 135 98 16 10
 146 204 70 11 39
 110 112 -- -- 41
 75 124 -- -- 32
 Number of plants 29 29 27 27 29
 Average height 111.7 117.2 99.1 63.4 28.5
 From Tables III an IV it can be seen that the method of the invention
 exerts a positive effect on the growing of the plants. In case of the
 control groups, the average height is very low on day 11, and even on day
 14, the control plants are considerably less developed than the plants
 treated according to the invention.
 It is to be mentioned that in an experiment maize plants grown from
 untreated seeds were sprayed with a solution of compound "A" of optimum
 concentration in the 3 weeks' state, and on the next day the plants were
 subjected to a frost treatment. In some hours the 15 plants examined were
 destroyed.

The above experiments prove that the composition of the invention is indeed
 suitable for the promotion of plant production and for the elimination of
 the unfavourable enrivonmental influences in plant cultivation.