CH617418A5 - Plant growth regulators. - Google Patents

Abstract

In plant growth regulators, the active ingredient used is a novel compound of the formula I <IMAGE> in which U, V, W, X, Y and Z independently of one another denote hydrogen, halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, NO2, CF 3, COOH, CN, OH, SO3H, NH2 or -NH(C1-C4-alkyl) or -N(C1-C4-alkyl)2, and where U and X additionally in each case can also represent an unsubstituted phenyl radical, and in which R denotes hydrogen or the cation of a base 1 DIVIDED n M<n(+),> where M denotes an alkali metal cation, alkaline earth metal cation or an Fe, Cu, Zn, Mn or Ni cation or an ammonio radical and <IMAGE> n as an integer 1, 2 or 3 takes into consideration the valency of the cation, while R1, R2, R3 and R4 independently of one another denote hydrogen, benzyl or a C1-C4 alkyl radical which is optionally substituted by -OH, -NH2 or C1-C4-alkoxy, with the proviso that, if R is hydrogen, at least one of the substituents U-Z must be other than hydrogen.

Description

       

  
 

** WARNING ** beginning of DESC field could overlap end of CLMS **.

 



   PATENT CLAIMS
1. Plant growth regulating agent containing as active component a new compound of formula I.
EMI1.1
 wherein U, V, W, X, Y and Z are independently hydrogen, halogen, C1-C4-alkyl, Cl-C4-alkoxy, C1-C4-alkylthio, NO2, CF3, COOH, CN, OH, SO2H, NH2 or -NH (C1-C4 alkyl) or -N (CI-Cs alkyl) 2, and where U and X can additionally each represent an unsubstituted phenyl radical, and in which R is hydrogen or
1 - the cation of a base - n, where M is an alkali, alkaline earth cation or an Fe, Cu, Zn, Mn,
Ni cation or an ammonio residue
EMI1.2
 and n takes into account the valence of the cation as an integer 1, 2 or 3,

   while R1, R2, R2 and R4 independently of one another are hydrogen, benzyl or a C1-C4 alkyl radical which is optionally substituted by -OH, -NH2 or C1-C4 alkoxy, with the proviso that if
R is hydrogen, at least one of the substituents
U to Z must be different from hydrogen.



   2. The use of the agent according to claim 1 for inhibiting plant growth.



   The present invention relates to a plant growth-regulating agent which, as active component, comprises a new 1, 2-diphenyl-cyclohex-1-ene-4-carboxylic acid derivative of the formula I.
EMI1.3
 contains, in which U, V, W, X, Y and Z independently of one another hydrogen, halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, NO2, CF2, COOH, CN, OH, SO2H, NH2 or -NH (C1-C4 alkyl) or -N (C1-C4 alkyl) 2, and where U and X can additionally each represent an unsubstituted phenyl radical, and in which R is hydrogen or
1 - the cation of a base - n, where M is an alkali, alkaline earth cation or an Fe, Cu, Zn, Mn,
Ni cation or an ammonio residue
EMI1.4
 and n takes into account the valence of the cation as an integer 1, 2 or 3,

   while R1, R2, R2 and R4 independently of one another are hydrogen, benzyl or, if appropriate, substituted by -OH, -NH2 or C1-C4 alkoxy
C1-C4 alkyl radical mean with the proviso that if
R is hydrogen, at least one of the substituents
U to Z must be different from hydrogen.



   The invention also relates to the use of the agent for inhibiting plant growth.



   The compound 1, 2-diphenyl-cyclohex-1-en-4-carboxylic acid, which can also be called 3,4-diphenyl-A3-tetrahydrobenzoic acid, is known [Liebigs Ann. 570, 201 (1950)]. Nothing is mentioned in the literature about a plant-influencing effect. This agricultural, technologically very favorable property is therefore completely surprising.



   The compounds of the formula Ia can be prepared, for example, by reacting acrylonitrile, acrylic acid or an acrylic ester with optionally a diene of the formula II



  be performed. [J. Org. Chem. 28, 2154 (1963)].



   An effective subgroup of compounds of the formula I are salts which are derived from the main body of this series of compounds, 1,2-diphenylcyclohex-1-en-4-carboxylic acid, in particular metal salts and lower alkylammonio or lower hydroxylalkylammonio salts.



   Another subgroup with interesting effects is those compounds of the formula I and their salts in which U, V, W, X, Y and Z are hydrogen, halogen, C1-C4 alkyl, C1-C4 alkoxy, methylthio, ethylthio, NO2, CF2, COOH, CN, OH, SO2H, NH2, methylamino, ethylamino, dimethylamino, diethylamino or methylethylamino and at least one of these substituents has a meaning other than hydrogen.



   The following example illustrates the preparation of the compounds of formula I. Parts mean parts by weight.



  Temperatures refer to degrees Celsius. Further connections are listed in the table below.



   Example 1 a) 1st variant
A mixture of 50 parts of 2,3-diphenyl-2,3-dihydroxybutane and 0.5 part of freshly dewatered KHSO4 is distilled at 11 torr and 200 bath temperature for 50 minutes. The fraction collected within the 150-180 / 11 Torr boiling range gives 43.8 parts of crude 2,3-diphenyl-1,3-butadiene. The product is stirred directly with 21.5 parts of acrylic acid and 2 parts of hydroquinone under N2 atmosphere for 3 hours at 130-140.



   The cooled reaction product is mixed with diethyl ether and extracted with 1N NaOH. The aqueous phase is concentrated with. HCI acidified and extracted with diethyl ether. The organic phase is dried over Na2SO4 and evaporated in vacuo. 21 parts of 3,4-diphenyl-a3-tetrahydro-benzoic acid are obtained. M.p. 136-1400.



   (Verb. No. 1).



  b) S. variant
A mixture of 7.2 parts of 2,3-diphenyl-2,3-dihydroxybutane, 3.2 parts of acrylic acid, 0.1 part of p-toluenesulfonic acid and 0.3 part of hydroquinone is dissolved in 12 parts of acetic anhydride for 25 minutes at 130 -140 C kept in the bomb tube. The solution is evaporated in vacuo and the oily residue is worked up as in a). 2.2 parts of 3,4-diphenyl-ha-tetrahydrobenzoic acid mp 136-1400 are obtained.



   The following salts, for example, can be produced from this compound:
Verb. Cation M
No.



   2 Na + mp> 250
3 72 Cu ++ mp.> 250
4Fe +++
5 ¸ Ni ++
6 2 Zn ++
7 ¸ Mg ++
8Ca ++
9 d3 N (CH3) 4
Verb. Cation M
No.



   10 fDNH2 (CH2-CH2-OH) 2 mp 80-870
11 e NH (CH2-CH2-OH) 2 mp 83-860
12 # N (nC4HD) 4 oil
13 (3NH3 (nC8Hl7) mp 98-990
14 (CH2) '3N-CH2-C6H resin
Compounds of the following formula can be prepared in the same way:
EMI2.1
    No.

  U V W melting point
15 4-Cl H H 170-180
16 3-CH2 H H 112-1160
17 4-CH3 H H 146-148
18 3-COOH H H
19 4-phenyl H H 150-155
20 2-Cl 4-Cl H
21 3-Cl 4-Cl H
22 4-C2H2 H H
23 2-Cl 3-Cl 4-Cl
24 4-nC4H9 H H
25 4-nC4H9O H H
26 4-SO2H H H
27 4-CN H H
28 4-N (CH2) 2 H H
29 3-NO2 H H
30 3-CH2O H H
31 3-CH2O 5-CH2O H
32 2-CH2 4-CH2 H
33 4-Br H H 135-140
Salts according to formula I can also be prepared by reaction with a corresponding inorganic or organic base.
EMI3.1




  or with a compound of formula IIa
EMI3.2
 take place (Proc. chem. Soc. 1963, 217), with the use of acrylonitrile or acrylic ester after ring closure a saponification to the free carboxyl group must be carried out.



   This process is usually carried out at atmospheric pressure or elevated pressure in the temperature range from 80-2000C, preferably 120-1500C, in solvents suitable for Diels-Alder reaction, such as hydrocarbons (benzene, toluene, xylenes) [cf. H. Wollweber Diels-Alder reactions, Georg Thieme Verlag Stuttgart, 1972]. However, the process can also be carried out in the absence of a solvent.



   When using compound IIa, the addition of dehydrating agents (elimination of 2 moles of water) is necessary for the intermediate formation of compound II.



  For dehydration, customary agents such as Al203, p-toluenesulfonic acid, KHSO4, acetic anhydride / Na acetate and others can be used.



  be used.



   The cyclohexene-carboxylic acids (R = H) thus prepared can be converted into salts in the customary manner with an appropriate base defined under formula I.



   Some of the precursors of the formula II or IIa are known or can be prepared by known methods, for example by - reaction of the corresponding benzine derivative according to Gri gnard
EMI3.3

EMI3.4
 [Bull. Soc. chim. France 43, 873 (1928)] - Dimerization of the corresponding acetophenone derivative a) electrochemically, b) by irradiation (h v), c) in the presence of Al powder
EMI3.5
 a) [J. At the. Chem. Soc. 75, 5127 (1953)] b) [Tetrahedron 25, 4501 (1969)] c) [J. Org. Chem. 37, 2367 (1972)].



   For the preparation of the asymmetrical compounds of the formula II or IIa, in which U, V and W have a different meaning than X, Y and Z, a Grignard reaction can advantageously be carried out in one or two reaction steps with diacetyl, according to the scheme
EMI3.6
  
The new active ingredients of the formula I or corresponding agents intervene in the physiological processes of plant development and can be used for various purposes which are related to the increase in yield, the easier harvesting and the labor savings in measures on plant crops. The various effects of these active substances essentially depend on the time of application (from the ripening stage of the plant) and on the concentrations used. However, these effects differ depending on the plant species.



   The preparation of 4-phenyl-cyclohex- (3 or 4) -en-1-carboxylic esters is disclosed in general form in a larger connecting group in DT-OS 1 900 658. Such compounds are said to have antifertility properties which make them appear suitable for rodent control. No information is given on plant effects. Such effects are therefore completely surprising for compounds of the formula I of the present invention.



   Plant growth is influenced with the new active ingredients of formula I or with the new agents. In addition, the support tissue of the stems is strengthened in treated plants. The formation of undesirable poultry shoots in various plant species, e.g. in the case of tobacco is reduced very much, e.g. vegetative growth inhibited in vines.



   By influencing the growth, the active compounds used according to the invention can significantly increase the crop yield of plants (e.g. fruits, seeds, leaves).



  For example, soybean plants and other legumes experience a reduction in vegetative growth in favor of generative growth, which results in an immediate increase in yield.



   Also to be emphasized is the possibility of using the agents according to the invention to trigger leaf fall in certain plants (cotton, young plants of trees and shrubs intended for dispatch). Thus, the harvesting of cotton plants is made considerably easier and the cleanliness of the harvested cotton capsules is increased if the cotton plants are first defoliated with the compounds of the formula I. In the case of plants intended for transplantation, the perspiration can be reduced by defoliation.



   The type of plant influencing which is in the foreground, however, is based on the special property of the compounds of the formula I in producing certain weeds to inhibit growth to such an extent that this is approximately equivalent to a herbicidal action and can be used in practice for this purpose. The application of the agents causes dwarfism or dwarfism for a number of mono- and dicotyledon weeds (Setaria, Alopecurus, Sinapis, Galium, etc.). This results in weed control which is particularly advantageous from the standpoint of cultivated soil conservation, in that, regardless of the crop growth, a uniform, low plant cover is maintained which counteracts soil erosion by wind or water.



  The pronounced selective action of the compounds of formula I, the important large crops, such as sugar beet, wheat, barley, rye and others, either leave them unaffected or even, as in the case of cereal crops, increase the kink resistance of the plant by slightly reducing the growth very interesting method of protecting crops from weeds.



  A particularly advantageous feature of the compounds of the formula is the strong, herbicide-like growth inhibition on wild oats (Avena fatua), which is one of the most important grass-like weeds in crops, especially in cereals. Wild oats are one of the most difficult to control weeds. It is only imperfectly controlled by a few herbicides, but not at all by the majority of the herbicides on the market.



   The inhibition of plant growth does not change the life cycle of the plant, which is determined by genetic properties, in the sense of a mutation.



   In connection with the reduction in the growth of grasses, the maintenance of pure grass plantings can be seen, as they are created as green areas, in residential areas, on industrial sites or on car roads, railway embankments or bank embankments of water bodies. In all of these cases, periodic cutting of the lawn or grass cover is normally necessary. This is not only very expensive in terms of manpower and machinery, but also poses considerable dangers for the personnel and road users involved in the transport sector.



   There is therefore an urgent need, especially in areas with large traffic networks, to maintain and maintain the turf necessary for consolidating hard shoulder and embankments on traffic routes, but also to keep them at a medium height during the entire growing season with simple measures. This is achieved in a very favorable manner by applying the agents according to the invention.



   The agents according to the invention can be applied simultaneously or successively to the surface to be treated with further agents. These can be fertilizers, trace element mediators or other preparations that influence plant growth. However, it can also be selective herbicides, insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, together with, if appropriate, further carriers or application-promoting additives.



   Suitable carriers and additives can be solid or liquid and correspond to the substances commonly used in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.



   For application, the compounds of the formula I can be present in the following processing forms: solid processing forms:
Dusts, grit, granules, coating granules, impregnation granules and homogeneous granules; Liquid processing forms: a) Active ingredient concentrates dispersible in water:
Wettable powders, pastes, emulsions; b) solutions.

 

   The content of active substance in such preparation forms or agents is generally between 0.1 to 95%, preferably between 1 to 80%. Application forms can be diluted down to 0.001%. The application rates are generally 0.1 to 10 kg ai / ha, preferably 0.25 to 5 kg ai / ha.



   The active ingredients of the formula I can be formulated, for example, as follows: Dusts: The following substances are used to produce a) 5% and b) 2% dusts: a) 5 parts of active ingredient
95 parts talc; b) 2 parts of active ingredient
1 part of highly disperse silica
97 parts of talc.



   The active ingredients are mixed and ground with the carriers.



  Granules: The following substances are used to produce 5% granules:
5 parts of active ingredient
0.25 part epichlorohydrin
0.25 part of cetyl polyglycol ether
3.50 parts of polyethylene glycol
91 parts of kaolin (grain size b, 3-0.8 mm).



   The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone, then polyethylene glycol and cetyl polyglycol ether are added. The solution thus obtained is sprayed onto kaolin, and the acetone is then evaporated off in vacuo.



  Wettable powder. For the preparation of a) 70%, b) and c)
25% d) 10% wettable powder, the following ingredients are used: a) 70 parts of active ingredient
5 parts of lignosulfonic acid sodium salt
1 part of dibutylnaphthalenesulfonic acid sodium salt
24 parts of silica b) 25 parts of active ingredient
4.5 parts calcium lignin sulfonate
1.9 parts champagne chalk / hydroxyethyl cellulose
Mixture (1: 1)
1.5 parts of sodium dibutyl naphthalenesulfonate
19.5 parts of silica
19.5 parts of champagne chalk
28.1 parts of kaolin c) 25 parts of active ingredient
2.5 parts of isooctylphenoxy polyoxyethylene ethanol
1.7 parts champagne chalk / hydroxyethyl cellulose
Mixture (1: 1)
8.3 parts of sodium aluminum silicate
16.5 parts of diatomaceous earth
46 parts of kaolin d) 10 parts of active ingredient
3 parts mixture of saturated sodium salts
Fatty alcohol sulfates
5 parts of naphthalenesulfonic acid / formaldehyde condensate
82 parts of kaolin.



   The active ingredients are intimately mixed with the additives in suitable mixers and ground on appropriate mills and rollers. Spray powder is obtained which can be diluted with water to form suspensions of any desired concentration. Such suspensions are very suitable for treating plants in order to influence growth and development.



  Emulsifiable concentrates: The following substances are used to produce a 25% emulsifiable concentrate:
25 parts of active ingredient
2.5 parts of epoxidized vegetable oil
10 parts of an alkylarylsulfonate / fatty alcohol polyglycol ether mixture
5 parts of dimethylformamide
57.5 parts xylene.



   Such concentrates can be used to prepare emulsions of any desired concentration by dilution with water, which are suitable for plant application in order to inhibit growth.

 

   Inhibition of growth in grasses (post-emergence method)
Seeds of the grasses Lolium perenne, Poa pratensis, Festuca ovina and Dactylis glomerata were sown in plastic trays with a soil-peat-sand mixture and watered normally. Weekly, the grasses that have accumulated are cut back to a height of 4 cm above the ground and then sprayed with aqueous spray liquors of the active compounds of the formula I 40 days after sowing and 1 day after the last cut. The amount of active ingredient was the equivalent of 5 kg of active ingredient per hectare. 10 and 21 days after application, the growth of the grasses was evaluated according to the following linear grading scale:
Grade 1 = strong inhibition (no further growth
Time of application)
Note 9 = no inhibition (growth like untreated control) Compound No. 2 10 12 14 plant Lolium perenne 6 6 4 2 Poa pratensis 2 3 1 1 Festuca ovina 2 2 1 1 Dactylis glomerata 2 3 2 1


    

Claims (2)

PATENT CLAIMS 1. Plant growth regulating agent containing as active component a new compound of formula I. EMI1.1 wherein U, V, W, X, Y and Z are independently hydrogen, halogen, C1-C4-alkyl, Cl-C4-alkoxy, C1-C4-alkylthio, NO2, CF3, COOH, CN, OH, SO2H, NH2 or -NH (C1-C4 alkyl) or -N (CI-Cs alkyl) 2, and where U and X can additionally each represent an unsubstituted phenyl radical, and in which R is hydrogen or 1 - the cation of a base - n, where M is an alkali, alkaline earth cation or an Fe, Cu, Zn, Mn, Ni cation or an ammonio residue EMI1.2 and n takes into account the valence of the cation as an integer 1, 2 or 3, while R1, R2, R2 and R4 independently of one another are hydrogen, benzyl or a C1-C4 alkyl radical which is optionally substituted by -OH, -NH2 or C1-C4 alkoxy, with the proviso that if R is hydrogen, at least one of the substituents U to Z must be different from hydrogen. 2. The use of the agent according to claim 1 for inhibiting plant growth. The present invention relates to a plant growth-regulating agent which, as active component, comprises a new 1, 2-diphenyl-cyclohex-1-ene-4-carboxylic acid derivative of the formula I. EMI1.3 contains, in which U, V, W, X, Y and Z independently of one another hydrogen, halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, NO2, CF2, COOH, CN, OH, SO2H, NH2 or -NH (C1-C4 alkyl) or -N (C1-C4 alkyl) 2, and where U and X can additionally each represent an unsubstituted phenyl radical, and in which R is hydrogen or 1 - the cation of a base - n, where M is an alkali, alkaline earth cation or an Fe, Cu, Zn, Mn, Ni cation or an ammonio residue EMI1.4 and n takes into account the valence of the cation as an integer 1, 2 or 3, while R1, R2, R2 and R4 independently of one another are hydrogen, benzyl or, if appropriate, substituted by -OH, -NH2 or C1-C4 alkoxy C1-C4 alkyl radical mean with the proviso that if R is hydrogen, at least one of the substituents U to Z must be different from hydrogen. The invention also relates to the use of the agent for inhibiting plant growth. The compound 1, 2-diphenyl-cyclohex-1-en-4-carboxylic acid, which can also be called 3,4-diphenyl-A3-tetrahydrobenzoic acid, is known [Liebigs Ann. 570, 201 (1950)]. Nothing is mentioned in the literature about a plant-influencing effect. This agricultural, technologically very favorable property is therefore completely surprising. The compounds of the formula Ia can be prepared, for example, by reacting acrylonitrile, acrylic acid or an acrylic ester with optionally a diene of the formula II ** WARNING ** End of CLMS field could overlap beginning of DESC **.