SE436568B - SUBSTITUTED N-PHENYL OR N-NAFTYL-2-PYRIDINON-5-CARBOXYLIC ACID AND USING IT TO REGULATE CEREAL PLANTS - Google Patents

Description

Ru is a hydrogen atom, an alkyl group having up to U carbon atoms, or a halogen atom, preferably a bromine or a chlorine atom, and R 5 is phenyl, naphthyl or phenyl substituted with one or two of the same or different substituents selected from halogen, (C 1 -C 6) -alkyl, (C 1 -C 3) -alkoxy and trifluoromethyl or naphthyl substituted by up to two of the same or different halo atoms.

According to a preferred embodiment of the invention, E1 is a methyl group, R2 is a carboxy group or a salt thereof, preferably alkali metal salt, R3 is a hydrogen atom or a methyl group, RA is a hydrogen atom or a halogen atom and R5 is a substituted phenyl group, where the substituents are preferably chlorine or bromine.

When H2 is a salt of a carboxy group, an alkali metal, alkaline earth metal or transition metal may form the cation. The ion can also be an ammonium or substituted ammonium group;

Among representative ex. on metal salt cations may be mentioned alkali metal cations such as sodium, potassium, lithium or the like, alkaline earth metal cations such as calcium, magnesium, barium, strontium or the like, or heavy metal cations such as zinc, manganese, copper, copper, ferric, ferrous, titanium , aluminum or similar ï =.

Among the ammonium salts may be mentioned those wherein the ammonium cation has the formula NZ -alkyl group, a (G3-G8) -alkenyl group, a (G3-C8) -alkyl, 1,1-group, a (G2-G8) -hydroxyalkyl group, a (C24-C8) -alkoxyalkyl group, a (G2-C6) -aminoalkyl group , a (G 2 -C 6) haloalkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted phenylalkyl group, having up to 4 carbon atoms in the alkyl moiety, an amino- or alkyl-substituted amino group, or either any of the groups Z1, Z2, Z5 and Z4 together; with the nitrogen atom forming a 5- or 6-membered heterocyclic ring, which optionally has up to an additional heteroacid, nitrogen or sve atom in the ring, and which is preferably saturated, such as a piperidine; morpholine, pyrrolidine or piperazine ring or the like, or any three of the groups Z1, Z2, Z3 and Z4 together with the nitrogen atom may form a 5- or 6-membered aromatic heterocyclic ring, such as a pyrazole or pyridine ring. the ammonium group contains a substituted alkyl, substituted phenyl or substituted phenylalkyl group, the substituents are usually chosen: KW 10 15 20 25 BO 35 7807006 -7 3 from halogen atoms, (C 1-8) -alkyl groups, (C 1 -C 4) -alkoxy groups, hydroxy groups, nitro groups, trifluoromethyl groups, cyano groups, amino groups, (C 1 -C 6) alkylthio groups, etc. Such substituted phenyl groups preferably have up to two such substituents, Representative examples of ammonium cations are ammonium, dimethylammonium, 2-ethylammonyl, 2-ethylhexyl - (2 -hydroxyethyl) ammonium, tris- (2-hydroxyethyl) ammonium, dicyclohexylammonium, t-octylammonium, 2-hydroxyethylammonium, morpholinium, piperidinium, 2-phenethylammonium, 2-methylbenzylammonium, n-hexylammonium, triethylammonium, trimethylammonium butyl) ammonium, methoxyethylammonium, diisopropyl- ammonium, pyridinium, diallylammonium, pyrazolium, propargylammonium, dimethylhydrazinium, hydroxiammonium, metoxiammonium, dodekylammonium, oktadekylammonium, 4-dichlorophenylammonium, 4-nitrobenzylammonium, benzyltrimethylammonium, 2-hydroxietyldimetyloktadekylammonium, 2-hydroxyethyldiethyloctylammonium, dekyltrimetylammonium, hexyl triethylammonium, 4-methylbenzyltrimethylammonium and the like.

Among the substituents (which may be the same or different) which R 5 may contain are alkyl groups having up to H carbon atoms, alkyloxy groups having up to N carbon atoms, halogen atoms such as fluorine, chlorine, bromine and iodine atoms and trifluoromethyl groups. R5 has up to two substituents, the most preferred of which are halogen atoms, preferably having at least one in the H-position, (C1-Cu) -alkyl groups, preferably 4-methyl, (C1-Cu) -alkoxy groups , preferably--methoxy and trifluoromethyl groups, preferably H-trifluoromethyl.

Typical compounds of formula I include: N- (4-chlorophenyl) -5-carboxy-4,6-dimethylpyrid-2-one, N- (3-chlorophenyl) -5-carboxy-4,6-dimethylpyrid-2- one, N- (4-bromophenyl) -5-carboxy-4,6-dimethylpyrid-2-one, N- (2-chlorophenyl) -5-carboxy-4,6-dimethylpyrid-2-one, N- (4 -iodophenyl) -5-carboxy-1 +, o-dimethylpyrid-z-one, N- (2-fluorophenyl) -5-carboxy-4,6-dimethylpyrid-2-one, N- (4-trifluoromethylphenyl) - 5-carboxy-4,6-dimethylpyrid-2-one, N- (4-methoxyphenyl) -5-carboxy-4,6-dimethylpyrid-2-one, N- (B-nitrophenyl) -5-carbox1-4, β-dimethylpyrria-α-one, N- (4-cyanophenyl) -5-carboxy-4,6-dimethylpyrid-2-one, N- (α-chlorophenyl) -5-carboxy-6-methylpyrid-2-one, N- (4-nitrophenyl) -5-carboxy-6-methylpyrid-2-one, N- (4-cyanophenyl) -5-carboxy-4,6-dimethylpyrid-2-one, 7H N- (5-ethoxyphenyl) -5-carboxy-6-methylpyrid-2-one, N- (4-methylphenyl) -5-carboxy-6-methylpyrid-2-one, N- (3,4-dichlorophenyl ) -5-carboxy-6-methylpyrid-2-one, N- (4-methyl-3-chlorophenyl) -5-carboxy-6-methylpyrid-2-one, N- (4-chlorophenyl) -5-carboxy 3,4,6-trimethylpyrid-2-one, N- (4-bromophenyl) -5-carboxy 4,6-diethylpyrid-2-one, N- (4-chlorophenyl) -5-carboxy-4,6-diethylpyrid-2-one, N- (4-bromophenyl) -5-carboxy-4,6-dipropylpyridine 2-one, N- (4-chlorophenyl) -5-carboxy-4-ethyl-6-methylpyrid-2-one, N- (4-trifluoromethylphenyl) -5-carboxy-6-ethyl-4-methylpyrid-2- one, N- (4-xylphenyl) -5-carboxy-6-ethylpyrid-2-one, N- (4-bromophenyl) -5-carboxy-6-propylpyrid-2-one, N- (4-chlorophenyl) - 5-carboxy-3,6-dimethylpyrid-2-one, N- (4-trifluoromethylphenyl) -5-carboxy-3,6-dimethylpyrid-2-one, N- (4-bromophenyl) -5-carboxy-6- methylpyrid-2-one, N- (3,4-dichlorophenyl) -5-carboxy-4,6-dimethylpyrid-2-one, N- (2-chloro-4-methylphenyl) -5-carboxy-4,6- dimethylpyrid-2-one, 5-bromo-N- (4-chlorophenyl) -5-carboxy-4,6-dimethylpyrid-2-one, 5-bromo-N- (4-fluorophenyl) -5-carboxy-4, 6-dimethylpyrid-2-one, 3-chloro-N- (2,4-dichlorophenyl) -5-carboxy-4,6-dimethylpyrid-2-one, 3-fluoro-N- (3-chlorophenyl) -5- carboxy-4,6-dimethylpyrid-2-one, 3-bromo-N- (4-trifluoromethylphenyl) -5-carboxy-6-methylpyrid-2-one, and agronomically acceptable salts of the above acids, N- (4-chlorophenyl ) -5-Carbomethoxy-4,6-dimethylpyrid-2-one, N- (4-fluorophenyl ) -5-carbethoxy-4,6-dimethylpyrid-2-one, N- (5-methylphenyl) -5-carbobutoxy-4,6-dimethylpyrid-2-one, N- (3,4-dichlorophenyl) f5-carbetoxy -6-methylpyrid-2-one, and N-phenyl-5-carbomethoxy-6-methylpyrid-2-one. Although the compounds of formula I may be prepared by any per se known method, e.g. As described in the literature, for the preparation of analogous compounds, suitable preparative routes are set forth below.

According to a first method, an acid chloride is condensed with the former; R 5 \, R f _ "" "" "_ '\ H' cool wherein R 6 is a hydrogen atom or an alkyl group, and R has the meaning given above: with an enamine of the formula (II) wherein the R, R 1 and R 5 have the meaning given above, to form a dihydropyridone of formula (III) wherein R 1, R 2, R 5, R 5 and R 5 are usually carried out in an inert solvent, such as ethyl ether, methylene chloride, benzene or toluene, at a temperature of from 0 to 100 ° C.

The dihydropyridone is then dehydrated in the presence of a dehydrating agent, such as 2,3-dichloro-5,6-dicyano-1,4-benzoquinone or the like. This reaction quinone, palladium on charcoal or N-bromosuccinimide. the reaction is usually carried out in an inert solvent, such as benzene, xylene or chlorobenzene, and at a temperature of from 50 to 25,000, to give a pyridone of the formula 6 R: R oo R \ _ / l \, / 2 1 S / " wherein R, R 1, R 5, H 5 and R 6 are as previously defined, the ester can then be converted to the corresponding acid or salt by conventional hydrolysis, for example by using an agent such as sodium or potassium hydroxide or the like, at room temperature or elevated temperature of up to 100 ° C.

According to a second preparative route for the preparation of compounds according to the invention, a pyrone of the formula (VI) is reacted in which R, B1 and R3 have the previously stated meaning, with an amine of the formula NH2-R5 This reaction is usually carried out in the presence of an acid catalyst, such as p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid or sulfuric acid, in an inert solvent such as chlorobenzene, toluene, xylene or cumene, or by using a 50% aqueous solution of acetic acid as the reaction medium, to give a pyridone of the formula (VIII) I i? '- N \\ R1 1.5 wherein R, R1, RB and R5 have the meaning given above. is usually carried out at a temperature of from 5 to 25,000. The free acid and its salts can then be prepared by conventional techniques.

The compounds of formula (I), wherein R 4 is a halogen atom ka; is prepared by reacting the corresponding 4-pyridones, wherein Ra is a hydrogen atom, with a halogenating agent such as bromine, chlorine, sulfuryl bromide or sulfuryl chloride. in a suitable inert solvent, such as ethylene dichloride or methanol, and at a temperature of from 0 to 10,000.

Illustrative compounds of formula (I) which have been prepared are set forth in Table I below, which also contains melting points and elemental analyzes. Following Table I are illustrative examples of preparations of some of the compounds in Table I, and in these examples all temperatures are given in OC while all parts and percentages are by weight, respectively. weight percent, unless otherwise stated.

This reaction is carried out as usual: Procedure No. 110 10 12 13 14 X 4 ~ Cl 4-Cl HH 4 ~ CH3 4-CH3 3,4-diCl1 3,4-diCl4-F 4-F 3-Cl 3 ~ Cl1 -CH 3 ~ C1 4-CH 3-Cl 31 3, 7807006 -7 'IABELQI I C33 Y 0022 N // \\\ 0 cH3 x _ glement analysis (calculated = upper: eden of numbers; _ found = lower rage; 2 ; H_ Wsmn. 0 HN x HH 358-9 60.55 4.36 5.06 12.77 60.85 4.42 4.99 13.07 H Na j> 300 56.10 3.70 4.67 11 , 83 55.29 3.78 4.73 11.65 HH 250-1 69.12 5.39 5.76 - 5.40 5.161 _ H Na 300 63 39 4 56 5 28 -:> 61:54 4, 78 5:18 .- HH 238-40 70.02 5.88 5.45 _ 70.14 6.02 5.29 - H Ha:> 300 64.51 5.05 5.02 _ "'HH 276- 7 53.87 3.55 4.49 22.72 54.02 3.54 4.32 22.68 H Na 296-7 50.32 3.02 4.19 21.22 45.25 3.17 4, 05 21.40 HH 260-1 64.36 4.63 5.36 7.27 63.89 4§59 5.53 7.07 H Na> 300 59.36 3.92 4.95 6.71 ~ 58.83 3.88 5.03 4.95 HH 254-5 60.55 4.36 5.04 12.77 60.03 4.31 5.05 13.63 H Na:> 30o 56.10 3.70 4, 67 11.83 53.57 8.75 4.46 11.45 -HH 247-51 61.75 4.84 4.80 12.16 61.61 4.88 5.27 12.24 H Na 00 54 29 4 56 4 22 10 66> 6 54:88 4223 4: 3 9 11:05 '7807006-7 Compound 1 No. 15 16 17 18 19 20 21 22 23 24 25 26 27 28' mABELL I Kfortsï) X 4-OCH3 4-OCHS 4-CF3 4-CF 4-Br 3 4-Br 4-01 ngfi. for; 4-cl na§-- tyïï 4-c1 1 4-Cl 4 ~ Br 4-Br 4-Br 4 ~ C1 LLSmp. CHNXHH 219-21 65.92 5.53 5.13 - 65¶52 5118 "H Na 295 ~ 8 - - - HH 230-2 57.88 3.89 4.50 18.31 _ 58.31 3.93 4.66 18.04 H Na) 3oo - - - HH 244-6 52.19 3.76 4.35 24.81 5 52.67 3 85 4.66 24.84 H Na> 3oo - - - - HH 264-6 65.96 4; 3l 4.27 10.82 65.68 4.27 4.41 11.03 H Na.> 3oo - - - Hr Na> 22o - - - - Br H 248-50 41, 92 2.77 3.49 39.85 42.06 2.72 3.91 40.33 Br Na 290 - ~ ~ H c2H5129-30 54.87 4.61 4.00 22.82 54.97 4.69 3.98 23.33 HY z / I CO 2 R N 0 CH 3 HH 271-73 59.21 3.82 5.31 13.45 59.17 3.76 5.71 13.49 10 15 20 25 30 55 40 9 Phloo-7 Example 1 Preparation of N- (4-chlorophenyl) -5-carboxy-4,6-dimethylpyrid-2-one (Compound 1, Table I) (a) 4-chloroaniline (48.4 g), p-Toluenesulfonic acid (4.7 g) and ethyl isodehydrate acetate (65 g) are suspended in the cumin (260 ml), the reaction mixture is refluxed and water is collected in a Dean-Stark trap. After 18 hours the reaction mixture is cooled and washed with dilute hydrochloric acid to remove excess 4-chloroaniline.

The cumene is then removed in vacuo to give crude 5-carbethoxy-N- (4-chlorophenyl) -4,6-dimethylpyrid-2-one as a residue as a dark brown oil. (b) The crude ester prepared under (a) above is suspended in a solution prepared by mixing methanol (500 ml) and water (500 ml) and 50% aqueous sodium hydroxide solution (50 g).

The solvent is then removed and the suspension is refluxed for 6 hours. in vacuo and replaced with water (1000 ml). Insoluble material is filtered off and discarded. The clear aqueous layer is then acidified with hydrochloric acid, and the precipitate formed is filtered and dried to give (after recrystallization from acetone) 55 g of a product, N- (4-chlorophenyl) -4,6-dimethylpyrid-2-one 5-carboxylic acid, m.p. of 258-90 (sönderde1n.).

Example Gel 2 Preparation of N- (4-bromophenyl) -5-carboxy-4,6-dimethylpyrid-2-one (Compound 19, Table I) Ethyl hydraacetate (20 g, 0.102 mol) and 4-bromoaniline (19.3 g, 0.112 mol) is dissolved in 50% aqueous solution of acetic acid (100 ml). The mixture is refluxed for 12 hours, after which the solvent is removed and the crude ester is isolated in the form of a brown oil.

The crude ester isolated above is heated for 6 hours with 500 g of 5% NaOH in methanol / water in the ratio 1: 1. diluted with water (100 ml) and filtered to remove insoluble matter. The mixture is cooled, material. A certain portion of the methanol is removed in vacuo, and an additional portion of water is added. then acidified, and the precipitate formed is filtered and dried.

Recrystallization from acetonitrile gives pure N- (4-bromophenyl) -5-carboxy-4,6-dimethylpyrid-2-one (5.3 g, 16.1% yield) with a melting point of 244-60 (dec.).

Example 2 Preparation of N- (4-bromophenyl) -5-bromo-5-carboxy-4,6-dimethylpyrid-2-one (Compound 25, Table I) Sodium -N- (4-bromophenyl) -4, 6-Dimethylpyrid-2-one-5-carboxylate (285 g, 0.00828 mol) is dissolved in dry methanol (50 ml). Bromine (1.59 g, The clear basic solution 10 15 25 30 55 40 ---- ~ - - '* --- ~~ f - 7807006-7 10 0,00994 mol, 1, 2 eq.) dissolved in methanol (50 ml) and added dropwise to the vigorously stirred brine over a period of 15-20 minutes. The solvent is then removed and the residue is taken up in dilute base.

After filtering off the insoluble material, the clear basic aqueous solution is acidified with hydrochloric acid. The precipitate formed is filtered and dried and recrystallized from acetonitrile to give N- (4-bromophenyl) -5-bromo-5-carboxy-4,6-dimethylpyrid-2-one (2.25 g, 67.8%). ) with a m.p. of 248-2500.

Example 4 Preparation of N- (4-chlorophenyl) -5-carboxy-6-methylpyrid-2-one (Compound 28, Table I) (a) Ethyl B-anilinocrotonate (23.9 g) is dissolved in dry benzene (200 g). Acryloyl chloride (10 g) is dissolved in additional dry benzene (200 ml) and added dropwise via an addition funnel with a side arm over the course of 1.5 hours.

The reaction mixture is allowed to stand at about 250 for 1 hour and then poured into water and extracted with methylene chloride. Expulsion 2? the solvent gives crude 5-carbethoxy-N- (4-chlorophenyl) -6-methyl-5,4-dihydropyrid-2-one (25.5 g) with a m.p. of 124-60 (from hexane / ether). (b) The ester (15 g) prepared under (a) above is dissolved in chlorobenzene: (500 ml). 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (25.2 g) is added and the mixture is refluxed for 3 hours. The reaction mixture is then cooled, then filtered and diluted with equal volume of methylene chloride and washed thoroughly with a dilute aqueous solution of sodium bicarbonate. The solvent is removed in vacuo and the residue of crude product is recrystallized from hexane / ether to give pure 5-carbethoxy-N- (4-chlorophenyl) -6-methylpyride-2-: L (8.3 g) with a m.p. of 55-40. (c) The pyridone (7.0 g) prepared under (b) above is suspended in a 5% aqueous solution of sodium hydroxide (200 ml). The mixture is heated in a steam bath for one hour, cooled and acidified with an aqueous solution of hydrochloric acid to give N- (4-chlorophenyl) -5-carboxy-6-methylpyrid-2-one (4.0 g) as when recrystallized from acetonitrile, m.p. of 271-50 with decomposition.

The compounds of formula (I) are especially useful as chemical gametocides in cereals, such as wheat, barley, corn, rice, sorghum, kidneys, oats, rye and the like. When used as a chemist: gametocides effectively cause high levels of sterility in the treated plants without causing significant inhibition of the growth of the treated plants. lO l5 20 25 ÉO 55 40 11 vaovoos-7 The compounds of formula (I) also cause other growth regulating effects, such as e.g. inhibition of seed formation of undesirable monocotyledons for weed control, control of flowering, control of fruit formation and inhibition of seed formation in non-cereal species, control of maturation and other related growth regulating effects.

When the compounds of formula (I) are used as growth regulators for plants, they are applied in an amount sufficient to give the desired effect on the plant without causing any undesirable or phytotoxic effect. When the associations e.g. are used as chemical gametocides, they are usually applied to the plants to be treated in an amount of from about 0.7 to about 22.8 kg / ml per hectare, preferably from about 1.4 to about 11.3 kg / hectare.

The amount applied varies depending on the crop being treated, the compound used for the treatment and similar factors.

A preferred way of applying a compound of formula (I) as a growth regulating agent to plants is by foliar application. When this method is used, the gametocidal activity is most effectively achieved when the compound is applied before meiosis and preferably after initiation of flowering. The compounds of formula (I) may also be applied by seed treatment, the seeds being immersed in a liquid preparation containing the active compound or the seeds being coated with the compound.) In seed treatment applications, the compounds are usually applied in an amount of from about 1 / Ä to about 10 kg / 100 kg seeds. The compounds can also be applied to the soil or to the water surface in rice crops.

The compounds of formula (I) may be used as growth regulators either individually or in mixtures. For example, they can be used in combination with other growth regulators, such as auxins, gibberellins, morphactins, ethylene release agents such as ethylene, pyridones, cytokinins, maleic acid hydrazide, succinic acid 2,2-dimethylhydrazide, choline and its salts, (2-chloroethyl) trimethylammonium chloride, triiodobenzoic acid, tributyl 2,4-dichlorobenzylphosphonium chloride, polymeric N-vinyl-2-oxazolidinones, tri- (dimethylaminoethyl) phosphate and its salts and N-dimethylamino-1,2,5,6-tetrahydrophthalamic acid its salts, 2,3-dichloroisobutyric acid and its salts and 3- (4-chlorophenyl) -6-methoxy-s-triazine-2,4- (1H, 5H) -dione.

Under certain conditions, the compounds of formula (I) may be advantageously used in conjunction with other agricultural chemicals, such as herbicides, fungicides, insecticides and plant bactericides. A compound of formula (I) may be applied to growth media or to the plants to be treated, either as such or, as is usual, as a component of a growth regulating composition. or a preparation which also comprises an agronomically acceptable carrier. By "agronomically acceptable carrier" is meant any substance which can be used to dissolve, disperse or disperse a compound in the composition without impairing the effectiveness of the compound and which in itself has no appreciable adverse effect on the soil, equipment, crop or agronomic the environment. Mixtures of compounds of formula (I) may also be used in any of these preparations. The compositions may be either solid or liquid compositions or solutions. Ex.fi: the compounds can be prepared in the form of wettable powders, emulsifiable concentrates, dusts, granules, aerosols or liquid emulsion concentrates. In such preparations, the compounds are extended with a liquid or solid carrier, and, if desired, suitable surfactants are incorporated.

Details betr. suitable compositions and other matters in connection with the present invention may be obtained from our Swedish patent application 78-01307-5.

The compounds of formula (I) may be applied in the form of sprays by conventionally used methods such as conventional hydraulic spray, air spray and dust. For low volume applications, a solution of the compound is usually used. The dilution and volume of application usually depend on such factors as the type of equipment used, the method of application, the area to be treated and the type of stage of development of the crop being treated.

The data given in Table II below show the gametocidal activity of typical compounds of formula (I), and these data were obtained by the following procedure.

A bait-brush variety (Fielder) and a bait-brush-free variety (Mayo-64) of spring wheat are planted in an amount of 6-8 seeds per 15.25 per pot containing a sterile medium of 3 parts by weight of soil and 1 part by weight of humus. The plants are allowed to grow under short-day conditions (9 hours) during the first 4 weeks in order for them to achieve good vegetative growth before flowering begins.

The plants are then transferred to long-term conditions (16 hours), which conditions are achieved by means of high-intensity lamps in greenhouses. The plants are fertilized 2, 4 and 8 weeks after planting with a water-soluble fertilizer (N 16%, P 25%, K 16%) in an amount of one teaspoon (approx. 5 ml) per 5.8 liters of water and are often sprayed with 10 7 25700 7807006-'7 the insecticide marketed under the trademark "Isotox" for the control of aphids and treated with sulfur dust to prevent the emergence of mold.

Test compounds are applied to the leaves of the female plants provided with bait bristles, when these plants reach the development stage with sharp leaves (step 8 on the Feeke scale). All compounds were applied in a carrier volume of 473 liters per hectare containing a surfactant, such as "Triton X-100", in an amount of 0.3 g / liter.

After the ear has developed but before the anthesis is placed 4-6 At the first signs of flower opening, two ears per pot are cross-pollinated, using the experimental method, with the male plant free from bait bristles.

As soon as the seeds become clearly visible, the axle length is measured and the number of seeds per axle is counted for both the axle in bags and the crossed axes. Male sterility is then calculated as the percentage inhibition of seeds obtained in the bags placed in bags by the ears per pot in bags to prevent crossing. treated the plants. After ripening, the seed is planted on crossed ears to determine percentage hybridization.

The actual sterility is calculated using the following formula: SC - St% sterility = X 100 see S = seeds / small ears in ears of control plants placed in bags c St = seeds / small ears in ears of treated plants placed in bags.

Table II summarizes typical results obtained when evaluating compounds of formula (I). A dash indicates that no determination of the value was made. 'z-Hovooe-v u, HABHLL 11 CH3 Y, /' -_ ~ "c02H 0 N CH3 Mä fl fHßkH / infw X 316123111161.. _____._________ X Y_12 __._ 2 .. 3152225113»: mi 0.281 mi 4-01 HH 100 100 100 96 _ _ _ 4-01 H Na 100 100 100 100 92 52 _ HHH 22 o 4 6 _ _ _ HH Na 46 0 13 8 _ _ _ 4_cH3 HH 21 0 0 14 13 12 2 4_cH3 H Na 0 0 o 14 11 2 3 3,4_dic1 H -H 98 93 80 12 20 16 12 3,4_dic1 H Na 96 91 33 22 25 21 4 4_F HH 0 0 0 9 0 24 13 4_F H Na 0 0 0 2 7 18 15 3-01 HH 4 0 0 0 3 3 2 3_c1 H Na 0 2 0 _ _ _ _ 4_cH3,3_01 HH 6 4 o 19 0 _ _ 4_cH3,3-01 H Na 0 2 1 0 1 6 _ 4_0cH3 HH 56 18- 2 9 - _ - 4-0cH3 H Ha 54 31 0 3 ~ - _- 4-CF3 HH 15 3 _ _ _ -_ _ 4_cF3 H Na 0 3 0 0 1 _ _ -4_Br HH 100 100 100. _ _ _ _ 4 -Br H HH 100 100 100 100 100 100 100 100 4-01 naphthyl 'HH 2 _ _ _ _ _ _ _ 4 ~ Cl naphthyl' H Na 14 4 0 0 - - - 4-01 Br H 9 7 9 16 13 - - 4-Cl Br Na 15 13 13 20 13 - _ 4-Br 4-Br 4-Br 4-Cl 4-01 15 TABLE II _ (cont.) 3; R fa .4, s Br H _ _ 'Br Na 100 99 H CZHS 100 XHH 100 88 H Na 100 100 90 39 22.5 1.2.5 0._ ~ __- 56 se 43 25 - 100 - 100 co2 R CH3 49 19 -

Claims (5)

A compound of the formula RÖ R "H2 \\, // If / / f \\ O / f N R1 wherein R2 is carboxy (or an agronomically acceptable salt thereof). or carbalkoxy having up to H carbon atoms in the alkoxy moiety, H 3 is hydrogen or (c 1 -C 4) -alkyl, H 1 R is hydrogen, (C 1 -C 6) -alkyl or halogen and H 5 is phenyl, naphthyl or phenyl substituted by one or two of the same or different substituents selected from haloene, (C1-Cu) -alkyl, (C1-Cu) -alkoxy and trifluoromethyl or naphthyl substituted by up to two of the same or different halo atoms. A compound according to claim 1, wherein R 5 is phenyl substituted with one or two halogen atoms. A compound according to claim 2, characterized in that R 1 is methyl, R 2 is carboxy or an alkali metal salt thereof, U is hydrogen and R 5 is phenyl substituted R 3 is hydrogen or methyl, R is chlorine or bromine. Ä. A compound according to claim 5, characterized in that Ru is hydrogen and R5 5. Use to regulate the growth of cerealí- is U-bromophenyl. plants, of a compound according to any one of claims 1 to U in an amount effective to cause male sterility in the plant. 7807006-7 SUMMARY The invention relates to novel compounds of the formula: 4 H3 R | H2 r I of N Ri å; wherein B1 is alkyl, H2 is carboxy (or an agronomically acceptable salt thereof) or carbalkoxy, H3 is hydrogen or alkyl, Ru is hydrogen, alkyl or halogen and H5 is a possible substituted aryl group. The new compounds show activity as plant growth regulators, especially as chemical gametocides. The invention also relates to growth regulating compositions comprising the novel compounds and methods for regulating the growth of plants with these compounds and compositions.