NZ207599A - Composition containing 3,6-diaminoacridine n-glycoside or acid addition salts thereof as plant growth regulators - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £07599 2 07599 »• • n , I Priority Daie(s): Complete Specification Filed: cuss: DEC 1986 Publication Date: ^ P.O. Journal, No: ..

NO DRAWINGS COMPLETE SPECIFICATION "PLANT GROWTH REGULATORS" *->WE BIOGAL GYOGYSZERGYAR of 4042 Debrecen, Pallagi ut 13., Ungarn, Hungary, a Hungarian company, hereby declare the invention, for which -i-/we pray that a patent may be granted to flneVus, and the method by which it is to be performed, to be particularly described in and by the following statement (fo! towed by page I A.) ... 207599 PLANT GROWTH REGULATORS e The invention relates to plant growth regulators, that is, compositions influencing the growth and development of plants. The compositions of the invention include as active agents a 3,6-diaminoacridine N-glycoside of the formula (I) (I) NH-R-, and/or its acid addition Bait of the formula (II) R2-ks NH-R, [A] fn) in which formulae at leaBt one of and R^ stands for an <t- and/or and/or «c- and/or /^- (L)-glucosyl, -galactosyl, -mannosyl, -xylosyl, -arabinosyl, -ribosyl, -6-desoxyglucosyl, -6-desoxygalactosyl, -ramnosyl, -maltoayl, -2-acetamido-2-desoxyglucosyl, -lactosyl, -cellobioeyl, -genciobiosyl or lamina-ribiosyl group and the other one represents either a hydrogen atom or one of the enumerated sugar groups; A. 3160-741/^0 ASOCTmtB A 1/ 207599 A is a residue of an acid; and p is equal to 1, 2 or 3.

The compounds of the formula (I) and their acid addition salts of the formula (II) are known from the 5 U.K. Patent No. 2,096,135 and U.S. Patent No. 4,462,993, their effect on the growth of plants is not known up to date.

Different processes like the selection of improved varieties, complex plant protection, improving of the <0 10 soil, fertilizing and watering are widely used in the agriculture for improving the yield and the quality of crops in general. A new possibility for increasing the yield of crops was opened by the use of plant hormones and, respectively, growth regulators /Turner 15 (1972), Outlook Agr. 7,14/.

The mechanism of the action of natural plant hormones was studied, and hormone-like acting substances were prepared on an industrial scale. These substances, e.g. auxins, gibberellins, cytokinins, aubBtances 20 deliberating ethylene, inhibitors etc. intervene in the life mechanisms of the plant and thus promote or delay the germination, growth, blooming and fructification of the plant, increase the resistance against frost and • dryness, inhibit the lodging of corn, increase the protein content-and the content of essential amino acida and so on /T. Dease (1978) World Farm 20, 8-9, 1415; ISOCTHis 207599 Farm Chemicals (1978) 141, 3, 42; Hungarian patent specification No. 175,568/.

The UBe of growth regulators do^s not only increase the yield of crops but influences their quality, too, 5 or possesses other agrotechnical advantages /Nickell, L.G. (1982) Plant Growth Regulators, Edn. Springer © Verlag Berlin-Heidelberg-New York; US-PS No. 4,116,675-Japanese patent specifieation Wo.—44,070/.

Despite the very promising possibilities of 10 application is the use of growth regulators in practice ■w' much less wide-spread than one would expect in view to the described advantages. About 70 % of the market of the plant growth regulators fall to 8 compositions; namely, most of the substances found up to now are growth 15 inhibiting substances (I.I.Batch: Plant Growth Regulators in Crop Management, Symposium on Bioscience, 20th to 21st April, 1982, Szeged, Hungary).

When the commercially available compositions are used in the practice, the following disadvantages are to 20 be expected: - in the case of the majority of the compositions the optimally usable quantity falls into a very narrow concentration range, that is, they can easily be "overdosed" and then the desired effect is not exerted; 25 - the success of the treatment depends on climatic factors, too; s - Jsocrmr ^ .•£ 1 v 2 07599 - in case of lignifying plants of several years the condition of the plant in the preceding year ia of decisive importance; - some of the regulators are efficacious only if 5 the treatment ia performed at a determined vegetative stage of the plant; and - the various species of plants react in a different manner on the growth regulators.

Finally, it ia a fact that actually remarkable 10 results were attained with plant growth regulators in garden and greenhouse cultivations but there is no actually efficacious stimulator for agriculturally important plants cultivated on large areas, e.g. for maize, soya, rice, wheat /T. Dease (1978) World Farm. 15 20, 8-9, 1415/.

The invention is based on the recognition that the 3,6-diaminoacridine N-glycoside derivatives of the formula (I) influence the growth of plants, first of all they exert a stimulating effect. This recognition is 20 surprising because there is no hint in the technical literature regarding the use of acridine derivatives as growth regulators in agriculture. Numerous acridine derivatives raise big hopes in cancer research and in u case of the known compounds of formula (I) only pharma- cological activities were observed up to the present-.

It was found that seed-corn and, respectively, seed ~!!C7 207599 bulbs treated with a compound of the formula (I) or (II) germinate by 1 to 5 days earlier than the untreated control. The degree of .stimulation depends on the plant species. In most of the cases the treated seed corns 5 germinate not only more rapidly but also significantly better, that is, the percentual germination (number of germs per 100 seeds) iB better what is of particular importance in case of a seed-corn the germination power of which suffered from storing.

Due to the treatment according to the present invention the development of the root is also more intensive, the total mass of the roots and the number of the side roots increase. The seed-leaves (cotyledon) and the following leaves have a more intensive green 15 colour and owing to their higher chlorophyll content the photosynthesis takes place probably more intensively.

By the more rapid germination and the stronger root formation the treated plants possess in most of the cages a higher green mass, too, and not only at the 20 beginning but, depending in caae ef caeh plant apeeiea in Q bo?c less diatineted degree, over the complete vegetation period. On the basis of these observations field experiments were performed which showed that the compounds according to the invention increase the crop. 25 Positive results were attained first of all in case of maize, rice, soya, sun-flowers, sugar beets, wheat, poppy and paprika.

ISOCT* W H 2 07599 o In addition to theae general observations more or less valid for all the examined plant species the following concrete effects can be stated at the individual species.

In case of legumes not only the root mass increased strongly but the cumber of the root bulbs, i.e. rhysobiums, too. In case of poppies the height of the plant was more regular and at the side sprouts there were flowers and, respectively, poppy-heads, too, wherefore the yield of 10 heads and poppy was increased. Since the alkaloida content was higher, too, significantly more alkaloida could be recovered. In the case of maize the number of the flower branchings increased. In the case of soya the number of the hull storeys was higher. In the case of rice 15 the ears were longer and contained more corns. Sugar beets and wheat showed a significantly higher chlorophyll content. At sun-flowers the stems were longer and thicker, the fruit-plate was bigger, the yield higher.

The complexity of the effect of the active agents 20 according to the invention is surprising. The known growth regulators well-distinguishably exert an action either on the root growth or on the sprout formation or on the development of the generative organs. The acridine derivatives of the formula (I) and their acid addition 25, salts of the formula (II) exert a complex stimulating effect on the whole plant. If e.g. rice is treated by * 207599 spraying before flowering, not only a more rapid ripening ia attained but the crop becomes bigger, too. Numerous growth regulators (e«g.—those doecPibed in the Hungarian patent apeeifioation JJo.—176,514 ) exert a yield increasing effect only by inhibiting the vegetative growth and thu9 enabling a bigger plant density. The active agents according to the invention inhibit in some cases the vegetative growth, too, (poppy, sun-flower), but at the same time they increase the number of the fruit bodies (head, fruit plate) and the concentration of such substances as e.g. the alkaloida.

Finally, a harmony between the genetically depending efficiency of the crop and the environment conditions can be created by using the compounds of the formula (I) and, respectively, their acid addition salts of the formula (II). The available possibilities in this respect are particularly obvious if one thinks at the big difference between the efficiency of a plant in a phytotron and under field conditions.

The compounds of the formula (I) are prepared according to the U.K. Patent No. 2,096,135 and U.S. Patent No. 4,462,993. The preparation of the acid addition salts, e.g. the hydrochlorides, hydrobromides, sulfates, phosphates, etc., of the formula (II) is partly described there or they can be prepared according to well-known methods. For influencing the plant growth mixtures of J 207599 r^. the compounds of the formula (I) and/or their acid addition salts of the formula (II) can also be used.

The plant growth regulators according to the invention include 0.01 to 95 per cent by weight of one or 5 more active agent(s) and in addition the usual carriers, auxiliary agents, fillers, extenders, etc. The active ageuta are converted to preparations, e.g. solutions, dusts, emulsions, suspensions, pastes, granules, etc. in a known manner. These preparations are generally 10 prepared by admixing the active agent (s ) with the carriers and/or auxiliary agents and optionally adding surface-active substances, stabilizers and other additives.

As carriers e.g. water; dimethyl sulfoxide; dimethyl 15 formamide; propyl alcohols; ethylene glycol; propylene glycol; hydrocarbons; chlorinated hydrocarbons; ketones like acetone or cyclohexanone; mineral oil fractions as well as mixtures of these solvents can be used. As solid carrier first of all minerals, rock meals, clays, 20 kaolin, talc, diatomaceous earth or organic substances, mainly wastes and by-products of the agriculture, e.g. leached beetroot slices, milled maize cob, can be used.

The active agents according to the invention are chemically stable and compatible and therefore they can 25 be used together with other active substances generally used in the agriculture, like microelements, insecticides 1ST? 10759 and fungicides.

The compositions of the invention contain, as already mentioned, 0.01 to 95 per cent by weight of one ore more active agent(s); a content of 0.01 to 70 per 5 cent by weight is preferred. The usual forma ready for <^3 use, e. g. spray or pickle, can be prepared by diluting the above-mentioned formulations.

The plant treating ia carried out in a known manner e.g. by pickling the seed-corn. The oickling "*** 10 is performed e.g. by submerging the seed-corn into a solution of the active agent; by pickling with a dry or wet powder; by spraying the pickle solution; or by fixing the pickle on the seed-corn with the help of an adhesive agent ''e.g. xanthan, see Merck Index IX, 15 compound No. 9719). The active agent gets into the earth together with the seed-corn and, if the seed-corn begins to take up water, into the seed-corn with a very good efficiency. For the pickling preferably 0.5 to 2.5 kg. of active agent are used for one metric ton 20 of the seed-corn.

Since the active agents according to the invention exert a systemic effect; too, they can be applied by pouring onto or spraying the emerged plants. In this way the plants can be treated in a controlled way after 25 the emergence in certain vegetation periods. The optimal time and optimal dose depend on each plant species and 4-- 2 07 99: can easily be determined by a person skilled in the art by a aeries of experiments. Owing to the low phyto-toxicity of the active agents a possi^1-? overdosing ia not dangerous. In case of the application by spraying 5 doaea between 0.1 kg. and 3.75 kg. per ha proved to be advantageous. The good solubility of the active agents according to the invention in fat- and wax-like substances makea the penetration into the plant easier. It can still be improved by penetration promoting 10 solvents, e.g. dimethyl sulfoxide.

The activity of the growth regulators of the invention was examined both in laboratory and field tests at numerous plant apeciea. The resulta described in the following test examples are average values of four 15 replications on small plots in a random arrangement. The identification of the tested compositions (I, II, III, IV and so on) corresponds to the numbering of the formulation examples wherein the preparation of the corresponding compositions ia described. 20 Example 1 Seed stimulation of maize fZea mays) in a laboratory test Prom formulations containing different active agents pickling liquids of an identical active agent content were prepared by diluting with water. Into 100 ml. 25 each of the treatment liquid 100 seeds each of dry maize seed-corn were merged at a temperature of 25 °C for 16 207599 houra. The dose corresponded to an application rate of 0.5 kg. of active agent per ton of aeed-corn.

The examination of the germination was performed according to ISTA (International Rules for Seed Testing; Proc. Int. Seed Teat. Asa. 1966, 31, 1-152). Accordingly, the treated aeed-corn waa stored at a temperature of 25 °C between seed papers wetted with water. The per-centual germination waa evaluated on the 4th day, the length of the aprout on the 7th day. The control waa treated by merging into tap water.

The results are summarized in Table 1. Every result is the average of 3 replications, that is, of 300 seeds.

Table 1 No. of formu- lation Active agent Germination (% ) on the 4th day Length of the sprout Tern. ) on the 7th day I 3,6-diff3-D-glucopyranosyl- 100 9.8 amino)acridine II 3-amino-6- ([3-D-glucopyrano-sylamino )acridine hydrochloride 93 7.1 III 3 , 6-di (<C -L-ramnopyranosal- amino )acridine 88 9.8 IV 3, 6-di (Jc-D-ribopyranosyl- amino )acridine 93 9.2 - •* V»iWA *%+.. 2 07599 Table 1 (cont. ) V 3.6-di (|3-lactopyranoayl- 86 9.6 amino)acridine VI 3-(P —D-glucopyranoaylamino )--6- foG -L-ramnopyranoaylamino )- acridine 100 9.7 VII 3,6-di (ft-D-glucopyranoayl-amino )-acridine and 3-amino-6- (ft-D-glucopyranoayl- amino )-acridine 100 9.8 Control (tap water) 85 6.4 Example 2 Seed-corn treatment of rice ("field teat) Rice (Oryza aativa) to be used for seeding waa merged into a solution prepared from compoaitiona VII for 15 17 houra. The active agent quantity correaponded to an application rate of 2.5 kg./lOOO kg. of the aeed-corn. The differences observed in the field teat in comparison to the control merged into tap water were as follows: time of emergence 5 days earlier number of plants per current metre by 7 % higher length of the ear by 10 % higher corn yield by 10.3 % higher The bigger number of plants on 1 metre points to the fact that the percentual emergence ia improved 25 under field conditiona, too.

.A . , J i 2 075 Example 3 Seed-corn treatment of sugar beets (field teat) Seed-corna of sugar beet (Beta vulgaris) were pickled dry by using composition XI in an application rate of 1.25 kg. active agent for 1 ton of seed-corn.

In comparison to the control the following differences were obgerved regarding the most important parameters: time of emergence 7 days earlier munber of leaves per plant by 31 3 higher length of the stem of the developed leaf by 39 "b higher width of the moat developed leaf by 54.6 % broader beet weight at the time of the harvest by 57 "£ higher harmful nitrogen content by 9 7a less yield of pure sugar by 41.7 ~/o higher Example 4 Seed-corn treatment of peas (field test) Peas (Pisum sativum) to be used for seeding vjere pickled by composition VII, by using 0.5 kg. of active 20 agent were used for 1000 kg. of seed-corn. In comparison to the control the following differences were observed: time of emergence by 6 days earlier I ^ beginning of flowering by 4 days earlier legume formation by 1 day earlier complete ripening by 6 days earlier 2 07599 period of "tenderness""^ by 10 dayg longer number of root bulbs (rhygobiuma) by 20 £ higher 1) - The tenderneaa ia a quality parameter during the production of tinned legumea. The period of tender-5 neaa begina with the pickability and is terminated when the seed begina to become mealy.

Exanple 5 Seed-corn treatment of poppy ("field teat) Poppy (Papaver somniferum) to be used for seeding 10 wag merged into a pickling liquid prepared from composition V for 16 hours. 0.51 kg. of active agent were used for 1000 kg. of seed-corn. In comparison to the control merged into tap water the following differences were observed: time of emergence growing high of the stick beginning of flowering end of flowering weight of the crude leaves 20 weight of the crude roots by 3 days earlier by 2 days later by 2 daya earlier by 2 days earlier by 32 % less by 21 y> less height of the plant in flowering atate number of the sprouts carrying a capaule ripening yield of capsules yield of poppy seed by 10 lea a by 32.3 7o higher by 2 dayg earlier by 32 % higher by 37 ya higher * 2 075 r^. alkaloida content baaed on the same quantity of capsules morphine content kodeine content tebaine content narcotine content narcotaline content by 107.1 % higher by 107.1 jo higher by 140 & higher by 52.7 £ higher by 64.7 ro higher by 84.5 -/o higher Example 6 Poat emergence treatment of soya ffield teat) Soya plants were treated in two-leaf atate by composition VIII by spraying until runr.ing-off. The application rate was 0.1 kg. of active agent/ha. In compariaon with the control the following differences were stated: height of the plants at the time of the harvest width of the leaves at the time of the harvest length of the leaves at the time of the harvest distance of the lowest legume from the soil number of the legume storeys dry root mass yield of green legumes number of the leaves at the time of the harvest in ?o of the maximal number of the leavea by 25 £ higher by 32.2 7o broader by 43.2 7o longer by 36 % higher nearly the double (1.931 by 37.3 6 £ higher by 33.7 higher 24.7 To more leavea remain on the plant until the harvest 1 2 07599 Example 7 Seed-corn pickling and ultrasonic treatment ftnaize; field test) Maize to be used for seeding was pickled with 5 composition I in an application rate of 0.2 kg. of active agent/1000 kg. of seed-corn and treated with ultrasound for 5 minutes (apparatus of type KLN, vibration head TI, delivered power: 0.7 W./cm^.). In relation to the control only treated with ultrasound ■-J 10 but not pickled the following differences were observed: time of emergence 2 days earlier biotic potential of the germ by 7 io higher height of the plant by 10 higher length of the leaf by 33 :'S higher width of the leaf by 28 % higher thickness of the stem by 8 ^ thicker number of the maize-ear/parcel by 3 & higher weight of 1000 corns by 16 ;6 higher corn/ear by 25 & more In the following some examples for the formulation of the compositions according to the invention are described . By "product form" a commercial formulation is meant which has to be diluted before use. Under "applica-o tion form" the composition ready for use is understood.

The Roman numbers of the compositions correspond to those indicated in the test examples. * 2 075 9 (Product form) I A composition is prepared from 50 per cent by weight of 3,6-di(0-D-glucopyranosyl-amino)acridine, 40 per cent by weight of dimethyl sulfoxide and per cent by weight of water.

Before use it is diluted to the desired concentration. (Product form) II per cent by weight of 3-amino-6-fp-D-glucopyra-r* 10 noaylamino )acridir.e hydrochloride, 1 per cent by weight of ?;ater and 94 per cent by weight of dimethyl sulfoxide are homogenized. Before use the composition is diluted to the desired concentration.

(Product form) III 12.5 per cent by weight of 3, b-ci («c -L-raranopyra- noaylamino )acridine, 65.0 per cent by weight of dimethyl sulfoxide and 22.5 per cent by weight of water 20 are homogenized. The composition is diluted by water to the desired concentration before use.

(Product form) IV 40 per cent by weight of 3 , 6-di (oC-D-ribopyranosyl-amino )acrid ine, 50 per cent by weight of dimethyl sulfoxide and per cent by weight of water 2 07599 are homogenized. Before use the composition ia diluted to the desired concentration.

("Product form) V per cent by weight of 3i6-di((J-lactopyranoayl-5 amino)acridine, 65 per cent by weight of dimethyl sulfoxide and 10 per cent by weight of water are homogenized. Before use the composition is diluted by water to the desired concentration.

(Product form) VI per cent by weight of 3-ffb-D-glucopyranosyl- amino )-6- («C -L-rarnnopyranosylamino )acridine , 3 per cent by weight of propanol and 67 per cent by weight of water 15 are homogenized. Before use the composition is diluted to the desired concentration by water.

(Product form) VII per cent by weight of 3» 6-di ((J-D-glucopyranosy-amino)acridine, 10 per cent by weight of 3-amino-6- (p-D-glucopyrano- sylamino)acridine, per cent by weight of ethylene glycol, 2 per cent by weight of dimethyl sulfoxide and Q 63 per cent by weight of water are homogenized. Before use the composition is admixed with a 1 per cent by weight solution of the polysaccharide if* * 207599 xanthan for one of the commercially available adhesive agents) in a weight ratio of 1 : 1 and then diluted with the aeed-corn to be treated to the desired concentration (kg. of active agent per ton of aeed-corn). 5 (Application form) VIII 3, 6-di ((J-E-glucopyranoaylamino )acridine J.01 'Ht.% dimethyl sulfoxide 1.00 water 98.99 'fft.fo The composition can directly be used for apraying 10 the planta.

(Product and application form) IX 3 , 6-di ((b-D-glucopyranoaylamino )acridine 95 •fft.fo talc 5 -Vt The composition is diluted at pickling with the 15 aeed-corn to be treated to the desired concentration. (Product foi;m) X 50 per cent by weight of 3,6-di (|5-E-glucopyranosyl- amino )-acridine and 50 per cent by weight of kaolin 20 are homogenized. Before use 2 per cent by weight of water are added to the composition and the latter is diluted with the seed-corn to be treated to the desired concentration.

(Product and application form) XI 25 3 , 6-di (/i-D-glucopyranoaylamino )acridine 70 NX .% talc 30 rYt.#

Claims (2)

2 07599 - 20 - Before uae the composition is diluted with the seed-corn to be treated to the desired concentration. C o o - 21 - 207599 What we claim ia:

1. A plant growth regulating composition comprising as active agent a 3»6-diaminoacridine N-glycoside of the formula (I) and/or its acid addition salt of the formula (II) 10 20 NH-R. (II) w r p p© 15 in which formulae at least one of R^ and R^ stands for an and/or 0-(D)- and/or •<:- and/or p- (L )-glucosyl, -galactosyl, -mannosyl, -xylosyl, -arabinosyl, -ribosyl, -6-desoxyglucosyl, -6-desoxygalactosyl, -ramnosyl, -maltosyl, -2-acetamido-2-desoxy-glucosyl, -lactoayl, -cellobiosyl, -genciobiosyl or -laminaribiosyl group and the other one represents either a hydrogen atom or one of the enumerated sugar groups; 25 A is a residue of an acid; and p stands for 1, 2 or 3. 207599 - 22 -

2. Plant growth, regulating composition as claimed in claim 1, characterized by containing as active agent "* S-di ((J-glucopyranosylamino )acr idine, 3-amino-6-([3-D-glucopyranosylamino )acridine hydrochloride, 5 3, b-di (cC-L-ramnopyranosylamino )acridine, 3,6-di(oC-D-ribopyranosylamino )acridine , 3, 6-di ((J-lactopyranosyl-amino)acridine, 3-(jJ-D-glucopyranosylamino )-6-(oC -L-ramnopyranoaylamino )acridine, 3-amino-6- ffi-D-glucopyra-noaylamino )acridine or the mixture thereof. 10 3- Plant growth regulating composition ag claimed in claim 1, characterized by containing 0.01 to 95 per cent by weight, preferably 0.01 to 70 per cent by weight, of active agent.;4. A method for influencing the growth of plants 15 characterized by treating the plant or a propagating part thereof with an effective amount of a 3,6-dianiinoacridine N-glycoside of the formula (I);20;R2-hn;(I);NH-R,;and/or its acid addition salt of the formula (II);25;^ —— ■ i. - — --■ —;—f V »;- 23 -;207599;IA]P° (II);F.g-HTJ;©;NH-R.;1;P;H;in which formulae at least one of R^ and R2 9tanda for an and/or £-(D)- and/or aC - and/or P>-(L )-glucosyl,;-galactosyl, -manruayl, -xylosyl, -arabinogyl,;-ribosyl, -6-desoxyglucoayl, -6-deaoxygalactoayl, -ramnoayl, -raaltosyl, -2-acetamido-2-deaoxyglucoayl, -lactoayl, -cellobioay1, -genciobiosyl or -laminaribiosyl group and the other one repreaents either a hydrogen atom or one of the enumerated sugar groups ;;A is a residue of an acid;;p stands for 1, 2 and 3.;5. A composition as claimed in claim 1 substantially as herein particularly described with reference to any one of the Examples.;BALDWIN, SON & CAREY;i* 150crv»<>