FI98813C - Cyclopropylmalononate derivatives and a composition comprising such a derivative for use in retarding plant growth - Google Patents

Description

98813

Cyclopropylmalononate derivatives and a composition comprising such a derivative for use in plant growth retardation 5 This application is divided by application 875280.

This invention relates to novel cyclopropylmalononate derivative compounds.

Some malonic acid derivative compounds have been known in the art for some time.

See, for example, U.S. Patent 2,504,896 and U.S. Patent 3,254,108. Some malonic-10 acid derivative compounds have been described in the prior art to be capable of producing certain plant growth regulating effects, such as fruit fall prevention, cuttings rooting and parthenogenetic fruit formation.

U.S. Pat. No. 3,072,473 describes N-arylmalonic acid half-amides and their esters and salts, Ν, Ν'-diarylmalonic acid half-amides, N-alkyl-N-alkylmalonic acid acid half-amides and their esters and salts, and N, N'-dialkyl -N, N'-diarylamalonic acid half-amides which can be used as growth regulators and herbicides. JP Patent 84,390,803 describes malonic acid anilide derivative compounds that can be used as growth regulators. The plant growth regulatory properties of substituted malonyl monoanilides are described by Shindo, N. and Kato, M. Meiji Daigaku 20 Noogaku-bu Kenkyu Hokoku, Vol. 63, pp. 41-58 (1984).

However, certain malonic acid derivative compounds and the use of malonic acid derivative compounds for growth retardation as described in this application have not been described in the prior art to date.

It is therefore an object of the present invention to provide a method of using cyclopropylmalononate derivative-25 female compounds to retard plant growth. Another object of the present invention is to provide novel cyclopropyl malonylate derivative compounds. These and other objects will be readily apparent to those skilled in the art from the following description.

The present invention relates to a novel cyclopropylmalononylate derivative having the formula: 98813 2 | 9 Y'7 Y'i0 -C — C-Υβ Z'n R'Vni -CCCn / Λ II \ = / (1) 0 0 r6 wherein: Z 'i 1 is the same or different and is one or more hydrogen, halogen, methyl, cyano or trifluoromethyl; Y'6 is hydrogen; Y’7, Y’8> Y’9 and γ, 10 are hydrogen; Y'41 is oxygen; and R "is already hydrogen or ethyl.

Formula 1 comprises a number of malonic acid derivative compounds. Examples of malonic acid derivative compounds of formula 1 10 that can be used to inhibit growth are shown in the following Tables 1 and 2.

table 1

Representative Malonic Acid Derivatives 15 Y’9 Y’7

I I

Yio -c —c — r8 zn OOY * 6 Y'7 | y'8 | y'9 [yio | Yfi Ικίο Ιζτι H_H_H_H_H_OH 3-F-4-C1_ H | h | h [HH [pH 3-Br-4 -Cl 98813 3

The specific compounds listed in Table 1 above are considered to be representative malonic acid derivative compounds that can be used to inhibit plant growth in accordance with this invention.

The malonic acid derivative compounds and intermediates included in formula 1 used in their preparation can be prepared by conventional methods known in the art and many of them are available from various suppliers.

The novel malonic acid derivative compounds can be prepared according to the following general reaction formula:

Y'g YV

I I

Y'10 -C —c — ra r „

\ / r ~ V

R ”10-Y’41 -C-C-C-Cl + HY6 —V A

il - y · ['

Y10 -C-c —Y'8 2 · ,,

Acid acceptor

--Γ-► R "io-Y'41 -C-C-C-Y'6-f A

10 -HCI j \ _ /

O O

Formula V

where Z '\\, Y * 6, Y'7, Y'8, Y'9, Y'10' Y <41 and R "10 are as defined above. This general type of reaction is carried out according to the malonic acid derivatives of formula (V). is prepared, for example, according to the Schotten-Baumann method known from Richter, GH, supra, with the conditions used in the process.

Preferred cyclopropylmalononylate derivatives according to the invention are the following compounds: 98812 4 V / r ~ \ CHaCH, -O-C-C-C-NH - (/ \ -Br I 8) = / o 0 CH: HO-C-C —C — NH— ¢ / Λ-Br 8 8/0 O CHj \ 7 HO-CC — C — NH — V \) - Cl 1 IV = / 0 0 CH3 \ 7, ΓΛ HO-CC-0 — NH— f ') -Cl

1 I W

0 0 Cl CH 2 CH 2 -C-C-S-C-NH-Cl 8 8) = 7

oof

HO-C - NH - C

1 I W

OOF HO C — S — C — NH—— Cl

I B W

0 o HO-C — 5 —— C — NH —- Br S I w 0 o HO-C — S — C — NH —- CF, 1 I w O 0 98813 5

Co-pending FI patent application 875279 describes synergistic growth regulating compounds comprising (i) an ethylene action or an ethylene-type action entraining agent and (ii) a malonic acid derivative compound of formula 1.

The cyclopropylmalononylate derivative compounds of formula 1 have been found to significantly retard plant growth compared to untreated plants under the same conditions. In addition, the compounds used in this invention are substantially non-phytotoxic to growing plants.

According to the present invention, an effective amount of a cyclopropylmalononylate-10 derivative compound to inhibit growth means an amount of a growth retardant effective to retard growth, this compound. The effective amount of the compound can vary within wide limits depending on the particular compound used, the particular plants to be treated, the environmental and weather conditions, and the like. The amount of compound used preferably does not cause substantial phytotoxicity, for example leaf blight, chlorosis or necrosis, to plants. In general, the compound can be applied to plants at a concentration of about 0.01-16.8 kg / ha (0.01 pounds to 15 pounds per acre), as described in more detail below.

The cyclopropylmalononylate derivative compounds of formula 1 can be used in many conventional ways known to those skilled in the art. Mixtures containing compounds as the active ingredient usually comprise a carrier and / or a diluent which is either liquid or solid.

Suitable liquid diluents or carriers include water-oil distillates or other liquid carriers with or without the addition of surfactants. Liquid concentrates can be prepared by dissolving one of these compounds in a non-phytotoxic solvent such as acetone, xylene, nitrobenzene, cyclohexane or dimethylformamide and dispersing the active ingredients in water with suitable surfactant emulsifiers and dispersants.

The choice of dispersing and emulsifying agents and the amount to be used are dictated by the nature of the mixture and its ability to facilitate dispersion of the active ingredient. In general, it is advisable to use such a substance as little as possible, according to the desired dispersion of the active ingredient in the syringe, so that the rain does not re-emulsify the active ingredient after application to the plant and rinse it off the plant. Nonionic, anionic or cationic dispersing and emulsifying agents such as condensation products of alkylene oxides and phenol, organic acids, alkylarylsulfonates, ether-alcohol-alcohol complexes, quaternary ammonium compounds and the like can be used.

In preparing wettable powder or dust mixtures, the active ingredient is dispersed in a suitable finely divided solid carrier such as clay, talc, bentonite, diatomaceous earth, effervescent water and the like. The above-mentioned dispersants as well as lignosulfonates can also be used in the preparation of wetting powders.

The required amount of active ingredient in question may be applied per hectare to be treated in 4.5 to 900 liters (1 to 200 gallons per acre) or greater than 10 volumes of liquid carrier and / or diluent, or in about 2.27 to 227 kg (5 to 5 kg). 500 lbs) inert solid carrier and / or diluent. The content in the liquid concentrate usually ranges from about 5% to 95% by weight and in solid preparations from about 0.5% to about 90% by weight. Satisfactory general purpose sprays or dusts contain from about 0.0005 to about 45 kg of active ingredient per hectare (from 0.001 lbs to about 100 lbs of active ingredient per acre), preferably from about 0.005 to about 6.8 kg of active ingredient per acre (from 0.01 lbs to about 15 lbs. active ingredient per acre), and more preferably from about 0.05 to about 2.27 kg of active ingredient per hectare (from 0.1 pounds to about 5 pounds of active ingredient per acre).

Formulations useful in the practice of this invention may also contain other optional additives, such as stabilizers or other biologically active compounds, as long as they do not inhibit or reduce the effect of the active ingredient and do not harm the plant being treated. Other biologically active compounds include, for example, one or more insecticides, herbicides, fungicides, nematicides, miticides, growth regulators, or other known compounds. Such combinations can be used for the known or other use of each additive and can provide a synergistic effect.

The cyclopropylmalononylate derivative compounds of formula 1 can be applied to plants under moderate or normal conditions. The compounds used in accordance with this invention may be applied during the vegetative growth phase of the plant or during the reproductive growth phase of the plant to retard plant growth.

Such compounds can be used in agriculture, horticulture and related fields and can generally be used on both bare-seeded and downy-seeded plants, especially plants such as woody plants and rotting grasses. For example, the compounds can be used to regulate growth height in roadside areas and to slow growth after oxalation of trees and shrubs and the like without any detrimental ecological effect.

As used herein, plants generally mean any agricultural or horticultural plants, woody plants, ornamentals or rotting grasses. Examples of woody plants that can be treated with the cyclopropyl malonylate derivative compounds of formula 1 by the process of this invention include e.g. red maple, cyclomor, red oak, american elm, lime, ginkgo biloba, oaks, wounds, maples, apple trees, chinese elm, wild apple trees, russian olive tree, silver maple, sugar maple, water oak, poplars, conifers and so on. Examples of other plants that can be treated with the compounds of formula 1 in accordance with this invention include corn, cotton, sweet potato, potato, blue-15 bat, wheat, rye, rice, barley, oats, sorghum, dried beans, soybeans, sugar beet, sunflower, tobacco , tomato, canola, deciduous fruit trees, citrus trees, tea, coffee, olive trees, pineapple, cocoa, banana, sugar cane, oil palm, herbaceous undergrowth, woody shrubs, rotting grasses, ornamentals, always vegetable plants, trees, flowers

20 The cyclopropylmalononylate derivative compounds in question have a growth retardant effect Such compounds have a very high safety margin because, when used in sufficient quantities to produce a growth retardant effect, they do not burn or damage the plant and are highly resistant to weathering, including rain flushing, decomposition. 25 ti light, oxidation, hydrolysis by moisture, or at least degradation, oxidation and hydrolysis which could actually reduce the desired growth retarding effect of the active ingredient or give the active ingredients undesirable properties such as phytotoxicity. If desired, mixtures of active compounds as well as combinations of active compounds with other biologically active compounds and additives can be used, as mentioned above.

The essential features of the invention are set out in the appended claims.

The following examples illustrate this invention.

8 98813

Example 1

Preparation of ethyl 1- (2-methyl-4,5-dichlorophenylaminocarbonylcyclopropanecarboxylate)

A round bottom glass flask purged with nitrogen was charged with 5.53 g (0.03 mol) of 2-5 methyl-4,5-dichloroaniline, 3.18 g (0.03 mol) of triethylamine and 190 ml of tetrahydrofuran solvent. With vigorous stirring, 5.55 g (0.03 moles) of ethyl 1-chlorocarbonylcyclopropanecarboxylate prepared in Example 5 was added in one portion, followed by stirring at room temperature for 6 hours. The triethylamine hydrochloride precipitate was then filtered off and the filtrate was distilled in vacuo to give a pale yellow solid. The solid was taken up in ether and the solution was washed with water, dried over magnesium sulphate and the solvent evaporated to give a yellow powder. Recrystallization from a mixture of ethyl acetate and hexane gave 4.51 g (0.01 mol) of ethyl 1- (2-methyl-4,5-dichlorophenylaminocarbonyl) cyclopropanecarboxylate, m.p. 105-107 ° C. The elemental analysis of the product-15 tea showed the following:

Analysis: C14H15Cl2NO3

Calculated: C: 53.18; H: 4.78; N: 4.43

Found: C: 53.41; H: 4.76; N: 4.44.

This compound is hereinafter referred to as compound 77.

20 Example 2

In the same manner as in Example 1, other compounds were prepared. Structural and analytical data for compounds 78-96 are shown in Table A below.

I: 98813 9

Table A

Representative malonic acid derivative compounds h2c-ch2 Z2 R'20-C-C-C-NH- /

O O

Substituents _Elemental Analysis_Melting ____Calculated__Approved_point

Compound R'2 Z'2 C H N C H N ° C

n ______ _78_C? Hs 2,4,5-Ch_ 46.38 3.59 4.16 46.69 3.99 4.10 130-132.5 79_C? Hs 3,4-Cl? _ 51.67 4 .34 4.64 51.95 4.34 4.72 107-110 _80_C? Hs 2,4-Cl? _ 51.67 4.34 4.64 51.27 4.53 4.46 95-98 _81_C? Hs 2,5-Cl 2 - 51.67 4.34 4.64 51.36 4.48 4.49 105-108 _82_C7H <; 2-F-4-Cl_ 54.65 4.59 4.90 54.92 4.71 4.85 94.5-96 _83_C7Hs 4-Cl_ 58.32 5.27 5.23 58.15 5.29 5 , 16 91-93 _84_C7Hs 4-Br_ 50.02 4.52 4.49 50.18 4.69 4.52 92.5-95 _85_C7Hs 3,4-Br7_ 39.92 3.35 3.58 40.18 3.47 3.60 128-130 _86_C7H <; 3,5-Βγ7_ 39.92 3.35 3.58 39.82 3.32 3.46 91-92.5 _87_C7Hs 2,4-Βγ7_ 39.92 3.35 3.58 40.02 3.61 3 , 77 102-103.5 _88_C7Hs 2-Cl-4-Br_ 45.04 3.78 4.04 45.28 3.98 3.90 109-110.5 _89_C7Hs 2-Br-4-Cl_ 45.04 3 .78 4.04 44.89 4.29 3.80 95-96 _90_C7Hs 3-Cl-4-Br_ 45.04 3.78 4.04 45.16 4.20 3.79 113-116 _91_C7Hs 2-CH7 -4-Br-5-Cl 46.62 4.19 3.88 48.14 4.74 3.86 119-121 92_C7Hs 2-F-4-Br_ 47.29 3.97 4.24 46.87 4 .07.02 102-103 _93_C7H5 H_ 66.83 6.47 6.00 66.54 6.48 5.80 85-89 _94_C? H ^ 3,5-Cl7_ 51.67 4.34 4.64 51 .52 4.52 4.36 64.67 95 _C? Hs 4-C = N_ 65.10 5.46 10.85 65.02 5.51 10.67 129-132 96] C? H <; | 2-CH7-4-Br 51.55 [4.94 4.29 ^ 1.72 U, 74 4.3 ^ 89-91 98813 10

Example 3 Preparation of H2-methyl-4,5-dichlorophenylaminocarbonylcyclopropanecarboxylic acid

A solution of 0.34 g (0.006 mol) of potassium hydroxide and 0.109 g (0.006 mol) of water in 80 ml of ethanol was prepared in a 250 ml round-bottomed flask. While cooling to 0 ° C in an ice / NaCl bath and stirring, 1- (2-methyl-4,5-dichlorophenylaminocarbonyl) cyclopropanecarboxylate prepared in Example 1 dissolved in a small amount of ethanol was added and the mixture was allowed to stir and warm to room temperature for 72 hours. The mixture was evaporated in vacuo to give a white solid which was dissolved in water and extracted twice with ether. The ether extracts were discarded. The aqueous solution was acidified to pH 2 with 25% HCl to give a solid which was taken up in ether and the acidified aqueous phase was extracted four times. The combined ether extracts were dried over magnesium sulfate and evaporated in vacuo to give a white solid. This white solid was washed with water and dried in a vacuum oven to give 1.85 g (0.006 mol) of 1- (2-methyl-4,5-dichlorophenylaminocarbonyl) cyclopropanecarboxylic acid, m.p. 248-251 ° C. Elemental analysis of the product showed the following:

Analysis: C12H11Cl2NO3 20 Calculated: C: 50.02; H: 3.85; N: 4.86

Found: C: 50.51; H: 4.31; N: 4.83.

This compound is hereinafter referred to as compound 110.

Example 4

In the same manner as in Example 3, other compounds were prepared. Structural and analytical data for compounds 111-128 are shown in Table B below.

II

98813

Table B

Representative malonic acid derivative compounds h2c — ch2 ζ · 4 \ / jf ~ y (

HO- |: -C-C-NH 2 SJ

o o

Substituent _Elemental Analysis_Melting-

Compound support__Calculated__Actual_point no Z'4_C_H_N_C_H_N_X_ 111 2-CHy4-Br 48.34 4.06 4.70 48.20 4.06 4.66 204.5-206 112 2.4.5-Ch_ 42.82 2.61 4 , 54 43.11 3.14 4.42 250_ 113 2.5-Cl? _ 48.20 3.31 5.11 48.33 3.26 4.96 223.5-226 114 2.4-07_ 48 , 20 3.31 5.11 45.26 3.40 5.03 189-190 115 2-F-4-Cl_ 51.27 3.52 5.44 51.18 3.70 5.22 202-204 116 4-Cl_ 55.12 4.21 5.84 54.69 4.35 5.59 217-219 117 4-Br_ 46.50 3.55 4.93 46.36 3.45 4.86 220-222 118 3,4-Br? _ 36.39 2.50 3.86 37.13 2.70 3.83 224-226.5 119 3.5-Br? _ 36.39 2.50 3.86 36.99 2.60 3.82 211-212 120 2,4-Br? _ 36.39 2.50 3.86 36.61 2.95 4.04 222-225 121 2-Cl-4-Br 41.47 2 .85 4.40 39.74 3.90 3.95 166-168 ________ (hair) _ 122 2-Br-4-Cl_ 41.47 2.85 4.40 41.67 3.28 3.91 210- 211 123 3-Cl-4-Br_ 41.47 2.85 4.40 41.70 3.23 4.11 211-214 124 2-CHy4-Br-5-Cl 43.33 3.33 4.21 45 .47 4.08 3.91 231-234 125 2-F-4-Br_ 43.73 3.00 4.64 43.97 3.05 4.30 203.5-207 126 4-Cfr; 75 [3.69 5.13 [52.73 3.90 [5.04 195-196.5 127 3.5-Cl 2 NMR (CDCl 3): 51.52 (s, 4H), 7.02-7, 74 198-202 __ (m, 4H) 10.08 (s, H) ppm ___ 128 3,4-Cb_ [48.20 3.31 [5.11 [48.79 3.80 [5.26 220-222.5 12 98813

Example 5

Preparation of ethyl 1-chlorocarbonylcyclopropanecarboxylate To a stirred solution of 15.1 g (0.27 mol) of potassium hydroxide in 240 ml of ethanol and 4.83 g (0.27 mol) of water was added dropwise, cooling to 0 ° C, 50.0 g (0.27 mol) of diethyl 1,1-cyclopropanedicarboxylate. The mixture was stirred for about 16 hours at room temperature. The solvent was removed under reduced pressure to give a white residue which was dissolved in water and extracted with ether. The aqueous solution was acidified to pH 2 with 25% aqueous hydrochloric acid and the organic acid was extracted from the aqueous suspension with ethyl ether (4 x 400 mL). The ether extract was dried over magnesium sulfate and evaporated in vacuo to give the monocarboxylic acid as a clear liquid. The clear liquid was dissolved in 300 ml of methyl chloride, followed by the addition of 74 g (0.62 mol) of thionyl chloride, and the resulting mixture was then heated under reflux for about 16 hours. The volatiles were removed in vacuo to give 45.7 g (0.25 moles) of ethyl 1-chlorocarbonyl-15-cyclopropanecarboxylate. NMR analysis of the product showed the following: NMR (CDCl 3): δ 1.22-1.50 (t, 3H), 1.75 (s, 4H), 4.1-4.52 (q, 2H) ppm.

This compound is hereinafter referred to as compound 155.

20

Example 6

Effect of representative svklopropwlimalonylate derivative compounds on plant growth retardation - field beans and wheat

Solutions of the test compounds identified in Table C were prepared by dissolving 68.8 mg of the title compound in 5.5 ml of acetone and then adding water to give a final volume of 11.0 ml. If turbidity occurred in the solution upon addition of water, the use of water was stopped and acetone was added so that the final volume became 11.0 ml. The resulting stock solutions contained 6255 ppm of the title compound by weight. Test concentrations in parts per million by weight of the final solution used in the "growth retardation experiments" shown in Table C were obtained by appropriate dilution of stock suspensions with acetone and water (50/50 v / v).

35 seeds of garden bean, wheat, wild wine, cucumber, sunflower, flax, buckwheat, tomato, perennial rye, calendula, soybean, chicken millet, wild oat and pea were sown in sandy clay soil on a platform measuring (width 8.8) 8.9 x length 20 cm (7.9 inches) x height 2.54 cm (1.0 inches).

li 9881? 13

Twelve to fourteen days after sowing, when the first three-leafed seedling of the field bean was at least 3.0 cm high, each test compound concentrate identified in Table C was applied by leaf spray to a single tray using a suction sprayer adjusted to 78.9 kPa (10 psig) -5 was applied at 4.48 kg / ha or 4 pounds / acre). For comparison, an aqueous acetone solution containing no compound was also injected into one platform. After the spray dried, all greenhouses were transferred to a greenhouse with a temperature of 27 ± 3 ° C (80 ± 5 ° F) and a humidity of 50 ± 5%. Visual signs of growth retardation were observed and recorded 10-14 days after treatment.

10 Visual observations of growth retardation were elucidated using a numerical scoring system. Numerical grades 0-10 were used to indicate the observed growth retardation compared to the untreated control. A score of 0 indicates no detectable effect, a score of 5 means that a 50% slowdown in growth was observed compared to the control, and a score of 10 means that the growth retardation was 100% compared to the comparator. A grade of 5 found in the same way means that the increase in plant growth is only half that found in the comparative experiment or that the plant has grown half the growth of the reference plant. This grading system shows any slowdown in plant height growth compared to untreated control plants. The results are reported in 20 Table C.

14 98813

Table C

Effect of representative compounds on plant growth retardation - field beans

Compound No. Growth retardation, grade 5 78 2 79 5 80 2 81 2 82 3 10 83 2 84 4 85 2 86 2 87 2 15 88 3 90 2 92 4 95 3 110 4 20 111 9 112 3 114 4 115 3 116 7 - 25 117 2 118 2 120 2 121 4 122 4 30 123 3 125 5 126 4 128 2 li 98813 15

Effect of representative compounds on plant growth retardation - wheat

Compound No. Growth retardation, grade 82 2 5 84 2 88 2 92 3 110 2 111 3 10 114 4 115 5 116 2 117 2 121 2 15 122 2 123 2 125 2 126 2 20 The results shown in Table C show that the growth of plants treatment with cyclopropyl limalonylate derivative compounds significantly slows plant growth compared to untreated plants.

Example 7

Effect of Representative Cyclopropyl Malonylate Derivatives on Growth Hi-25 Growth - Wheat

In the following Table D, unitized test compounds were prepared by dissolving the compounds in acetone / water (50/50 v / v) containing 0.05% v / v Triton X-100 surfactant sold by Rohm and Haas Company, Philadelphia, Pennsylvania. , USA. As described in detail below, these test compound solutions were sprayed on wheat at concentrations of 0.56 kg active ingredient / ha (0.5 pounds active ingredient per acre) or 1.12 kg active ingredient / ha (1.0 pounds active ingredient per acre).

Wheat seeds were sown in sandy clay soils in pallets the following sizes: width 8.89 cm (3.5 inches) x length 20 cm (7.9 inches) x height 2.54 35 cm (1.0 inches). Eight days after the wheat had entered the 2-3 leaf growth stage, each of the test compound concentrations identified in Table D was injected into 16,98813 single trays by leaf spraying using a vacuum injector set at 78.9 kPa (10 psig) (all trays injected at 1122 L). / hectare or 120 gallons / acre). For comparison, a water-acetone solution was also injected into one platform. which did not contain any test compound. After the spray dried, all wheat trays 5 were transferred to a greenhouse at 27 ± 3 ° C (80 ± 5 ° F) and 50 ± 5% humidity. Visual signs of growth retardation were observed and recorded 10-14 days after treatment.

Visual observations of a slowdown in growth were recorded using a percentage-based assessment. These percentage points 0-100 were used to indicate the observed 10 growth retardation rates compared to untreated control wheat. 0% means that no detectable effect was visible, 50% means that the increase in wheat growth was only half the growth of the reference wheat, and 100% means the maximum effect. This evaluation system shows a slowing of the overall height growth of wheat compared to untreated reference wheat.

15 The results are reported in Table D.

Table D

Effect of Representative Cyclopropyl Malononate Derivatives on Plant Growth Retardation - Wheat

Compound No. Quantity (pounds / acre) Growth retardation by 20%

Comparison - 0

Compound 96 0.5 30 1.0 40 25

Compound 111 0.5 60 1.0 70

Compound 114 0.5 20 30 1.0 30

Compound 82 0.5 10 1.0 10 35 Compound 115 0.5 30 1.0 40 li 98813 17

Table D (continued)

Compound No. Amount (pounds / acre Growth retardation as a percentage 5 Compound 116 0.5 40 1.0 70

Compound 117 0.5 50 1.0 60 10

The results in Table D show that treatment of plants with cyclopropylmalonium derivative derivatives results in a significant growth retardation compared to untreated control wheat.

15 Example 8

Effect of representative cyclopropyl malonylate derivatives on growth retardation - red maple and plane tree

The test compounds identified in Table E below were prepared by dissolving the compounds in acetone / water (50/50 v / v) containing 0.1% to 20% by volume of Triton X-100 surfactant sold by Rohm and Haas Company, Philadelphia, Pennsylvania. , USA. As explained in detail below, these test compound solutions were sprayed on red maple and plantain at concentrations of 1.12, 2.24 or 4.48 kg active ingredient / ha (1.0, 2.0 or 4.0 pounds active ingredient per acre).

25

Seedlings of red maple (Acer rubrum) and sycamore (Platanus occidentalis) were purchased and grown in 4.5-liter (one-gallon) plastic containers with sandy clay soil. Seedlings were maintained in a greenhouse at 27 ± 3 ° C (80 ± 5 ° F) and 50 ± 5% humidity. After one month, the growing seedlings were pruned to leave one main shoot 10.16-15.24 cm (4-6 inches) long. At this point, each of the test compound concentrations identified in Table E was sprayed onto individual trees as a leaf sprayer using a vacuum sprayer set at 78.9 kPa (10 psig) (all trees sprayed at 1122 L / ha, or 120 gallons / acre). For comparison, some trees were injected with an aqueous-acetone solution that now does not contain any test compound. Once the sprayer had dried, all the trees were transferred back to the greenhouse for a month. At this time (one month after treatment), visual evidence of growth retardation was observed and recorded.

98813 18

The percentage of shoot growth retardation shown in Table E was determined by measuring the shoot of each tree and comparing it to an untreated control tree. The average shoot length in untreated trees was 48 cm in red maple and 53 cm in plantain. The results in Table E represent the average of 3 replicates.

5 Table E

Effect of representative compounds on plant growth retardation - red maple and plane tree

Compound No. Amount (pounds / acre) Slowing of shoot height growth

Red Maple Plane 10 Comparison - 0 0

Compound 96 1.0 34 15 2.0 40 16 4.0 43 20 15

Compound 111 1.0 76 77 2.0 97 84 4.0 97 88 20 The results in Table E show that treatment of red maple and plantain with cyclopropylmalononate derivative compounds provides a significant growth retardation compared to untreated control red maple and plantain.

Example 9 Effect of Representative Cyclopropyl Malonylate Derivatives on Growth Retardation - Red Maple and Plane

In the following Table F, unitized test compounds were prepared by dissolving the compounds in acetone / water (50/50 v / v) containing 0.1% v / v Triton X-100 surfactant sold by Rohm and Haas 30 Company, Philadelphia, Pennsylvania, USA. . As explained in detail below, these test compound solutions were sprayed on red maple and plantain at concentrations of 1.12 or 2.24 active ingredients / ha (1.0 or 2.0 pounds active ingredient per acre).

Acer rubruml and Platanus occidentalism seedlings were purchased and grown in 4.5 liter (one gallon) plastic containers with sandy loam. The seedlings were kept in a greenhouse at 27 ± 3 ° C (80 ± 5 ° F). 98813 19 After 24 months, each of the test compound concentrations identified in Table F was sprayed onto individual trees as a leaf spray using a vacuum sprayer set at 5 to 78.9 kPa. 10 psig) (all trees were sprayed at 1122 L / ha, i.e. 120 gallons / acre.) For comparison, some trees were sprayed with an aqueous acetone solution containing no test compound, and after the spray was dried, all trees were transferred back to the greenhouse for 45 days. In this case (45 days after treatment) visual evidence of slow growth was observed and were recorded.

The percentage of new shoot growth retardation shown in Table F was determined visually by looking at the regrowth of each tree compared to the untreated control tree. A score of 0% means that no observable effect was seen, 50% means that the increase in tree growth was only half the increase in growth of the reference tree, i.e. that the tree had grown half the growth of the reference tree, 15 and 100% mean maximum effect. The results in Table F represent the average of 3 replicates.

Table F

20 Compound No. Amount (pounds / acre) Growth retardation

Red maple Plane

Comparison - 0 0 I Compound 96 1.0 47 8 25 2.0 42 9

Compound 111 1.0 85 43 2.0 91 46 30 The results in Table F show that treatment of red maple and plantain with cyclopropylmalononate derivatives provides a significant growth retardation compared to untreated control red maple and plantain.

Claims (3)

1 I Τ '* oo f HO C — S — C — NH — f ~ S Cl I s w o o HO — cS — C — NH —— Br 20 j | W 0 O 25 HO-C-S-C-NH-0-CF, O o 1 I / 0. CH, Cl HQ_rS-C-NH - ci 1 i o CH 2 Li 98813 HO-C-S-C-NH-Cl i i 0. Cl 5 CH, CH, -C Z-C-C-C-NH-Cl 1 0. F 10 HO C — S — C — NH— Cl 1. Cyclopropylmalonanilate derivative, characterized in that it has the formula: P Γ Y'iO -CC-Y'8 Z'n R different and are one or more hydrogen, halogens, methyl, cyanoylsyl trifluonomethyl groups; Υβ is hydrogen; Y'7, Y'8> Y'9 and Y10 are hydrogen; Y'41 is oxygen; and R 10 is hydrogen or ethyl. Cyclopropyhnalonanilate derivative compound according to claim 1, characterized in that it has the formula: CH 2 CH 2 O Composition for delaying growth of plants, characterized in that it comprises an acceptable carrier and an effective amount sufficient to delay growth of plants of the active substance according to claim 1 or 2.