CZ219487A3

CZ219487A3 - Plant growth retarding agent

Info

Publication number: CZ219487A3
Application number: CS872194A
Authority: CZ
Inventors: David Treadway Manning; James Joseph Cappy; Raymond Michael See; Anson Richard Cooke; Charles David Fritz; Thomas Neil Wheeler
Original assignee: Union Carbide Agricult
Priority date: 1986-03-31
Filing date: 1987-03-30
Publication date: 1994-05-18
Also published as: DD264372A5; RU2088571C1; UA26982A1; IE870808L; IE64777B1; NZ219815A; IL82053A; ES2004911A6; ZA872316B; CZ279071B6

Description

Uf1 / - fjL _ 1 - 2 -

Plant growth retardant Technique region i

° 1S00

BACKGROUND OF THE INVENTION The present invention relates to compositions for retarding growth of malt-derived plant. / i

Dosavadní_stav_techniky

Certain malonic acid compounds are already known for some time (see, for example, U.S. Patent No. 2,504,896 and U.S. Pat. No. 3,254,108). Some malonic acid compounds have already been described as being able to regulate plant growth < RTI ID = 0.0 >< / RTI > to prevent fruit falling, stimulate rooting of cuttings and form parthenogenetic fruits.

U.S. Pat. No. 3,072,473 discloses N-aryl maleamic acids and their esters and salts, N, N ' -diarylmalonamides, N-alkyl-N-arylmalonamic acids and their esters and salts, and N, N ' -Diarylmalonamides, which may be useful as plant growth regulators and herbicides. Japanese Patent Specification No. 84 39 803 (1984) discloses compounds derived from malonic acid which may be beneficial as plant growth regulators.

The growth regulating ability of substituted malonyl monoanilides is described by Shindo N. and Kato M. in Meiji Daigaku Noogaku-bu Kenkyu Hokoku, Vol. 63, pages 41-58 (1984).

The essence of the invention.

The object of the invention is to provide novel compositions based on malonic acid acting as plant growth regulators (retarders). In nnnlnrln " In order to slow down the growth of the grate, the present invention relates to a process for slowing down the growth of grates. > in < 9 / £? T < / < ts,

characterized in that it comprises as active substance a compound of formula (I)

wherein is hydrogen or C 1 -C 3 alkyl, Y 1 and Y 2 X are each hydrogen or together with the adjacent carbon atom form a cyclopropane or cyclobutane group, is oxygen or NH, is halogen, trifluoromethyl or methyl and a is 0, 1, 2 or 3, provided that when n is greater

than 1, the substituents X are the same or different. Preferred compositions of the invention contain as active ingredients the compounds of the formulas below: 4

ch3ch2 - O

Cl

- 7 - 9 - \ t

HO - C - C ti

O c If o

CH 3 CH 3 CH 2 - o - CH 3 CH 2 - o

10 -

Malonic acid derivatives corresponding to the above general formula (I) as well as intermediates used in their preparation can be prepared by methods known per se. In addition, many of the starting materials and intermediates are commercially available. The preparation of compounds of formula I is illustrated, for example, by the following reaction scheme, in which the general symbols are as defined above.

Rj = O-CO-CH2

acid acceptor - HCl

Reactions of this general type, including reaction conditions, have been described, for example, by Richter GH in Textbook of Organic Chemistry, 3rd Edition, John Wiley and Sons, New York, p. 486. The Schotten-Baumann reaction described in this publication uses cold acid acceptor as the acid acceptor. Aqueous sodium hydroxide solution. A similar procedure can be used to prepare compounds of formula I wherein Y 1 and Y 2 together with the carbon atom to which they are attached form a cyclopropane or cyclobutane ring, as well as the corresponding compounds wherein R 1 is NH.

Other procedures for the preparation of compounds of formula I and intermediates for their preparation are described, for example, in the following publications: Breslow DS et al., Jour. Amer. Soc. J56, 1286-1288 (1944); Svendsen A. i Hurts PM, Jour. Grg. Chem. 40, 1927-1932 (1975); Sen AK and Sengupta P., J. Ind. Chem. Soc. 46, (9) 857-859 (1969); Thiers R. and Van Dormael A., Bull. Soc. Chim. Belg. 61, 245-252 (1952); Brown RPC, Austral. Jour. of Chem. 13, 121-124 (1955); U.S. Patent No. 3,951,996; British Patent No. 1,374,900; Chiriac CI, Revue Romaine de Chimie 25, (3), 403-405 (1980); Weiner N., Org. Son. Coll., Vol. II, 279-282 (1950), Sixth Frinting, John Wiley and Sons, New York; Block Paul, Jr., Org. Son. Coll. Vol. V, 381-383 (1973); John Wiley and Sons, New York; Reliquet F. et al., Phos. and Sulfur 24, 279-289 (1985); Palmer CS and McWherter PW, Org. Son. Coll. Vol. I, 245-246 (1951), Second Edition,

John Wiley & Sons, New York; Straudinger H. and Becker H., Berichte 50, 1016-1024 (1917); Purrington ST and Jones WA

Synthesis J. Org. Chem. 48, 761-762 (1983); Kitazume T. et al., Chem. Letters (1984) 1811-1814; Wolff IA et al., 12 - (1984), 732-734; Zambito AJ and Howe EE, Org. Son.

Coll. Vol. V, 373-375 (1973); John Wiley and Sons, New York; Hartung WH et al., Org. Son. Coll. Vol. V, 376-378, John Wiley and Sons, New York.

Still other illustrative methods that may be used to prepare malonic acid-derived compounds corresponding to Formula I and intermediary compounds useful in the preparation of final compounds are described in, for example, the following publications:

Rathke MW and Cowan PJ, J. Org. Chem. j > 0, 2622-2624 (1985)} Bring WS, Org. Son. Coll. Vol. IV, 293 (1963)

John Wiley & Sons, New York; Gompper R. and Topfl W.,

Chem. Ber. 22 * 2861-2870 (1962); Gompper R. and Kunz R.,

Chem. Ber. 22 * 2900-2904 (1966); Ono N. et al., J. Org. Chem. 50, 2807-2809 (1985); U.S. Patent No. 4,154,952; Blankenship C. and Paquette LA, Synth. Comm. 14, (11), 983-987 (1984); Baldwin JE et al., Tet. Lett. 26, (4), 481-484 (1985); Kawabata N. et al., Bull. Chem. Soc. Jpn. 55 (8), 2687-2688 (1982); Bodanszky M. et al. Vignaud V, J. Am. Chem. Soc. 81, 5688-5691 (1959); Neelakantan S. et al., Tetrahedron 21, 3531-3536 (1965); U.S. Patent No. 4,020,999; Japanese Patent Application No. 148,726 (1979); Fuson RC, Advanced Organic Chemistry, p. 202 (1950)

John Wiley & Sons, New York; Duty RC, Anal. Chem. 49, 13- (6), 743-746 (1977); G., Contraai, AHi acad. Lincei 22y T. 823-836 (CA 8 73 (1914)), Schimelpfenig CW, J. Chem. Soc. Park. Trance. I, 1977 (10), 1129-1131;

Kim YS et al. Taehan Hwahak Hoechi 18, (4), 278-288 (1974); German Patent No. 2,449,285; U.S. Pat. No. 3,962,336; and US / 3 992 189 ·

Malonic acid-derived compounds of formula (I) significantly slow down the growth of plants compared to untreated plants under similar conditions. In addition, malonic acid compounds of the invention are essentially non-phytotoxic to growing plants. An effective amount of a compound of the invention sufficient to retard plant growth may vary over a wide range depending upon the particular compound employed, the plant to be treated, environmental conditions, climatic conditions, and the like.

The applied amount of active ingredient preferably does not induce substantial phytotoxicity, such as leaf burn, plant chlorosis or necrosis. Typically, the compound may be applied to the plants at a concentration of from about 0.01 kg / ha to 17 kg / ha as described in detail below.

Malonic acid-derived compounds corresponding to Formula I can be used in a variety of conventional ways known to those skilled in the art. 14 -

Compositions containing these compounds as active ingredients will usually contain a carrier and / or diluent, either liquid or solid.

Suitable liquid diluents or carriers include water, petroleum distillates or other liquid carriers either with or without surfactant. Liquid concentrates may be prepared by dissolving one of the disclosed compounds in a non-phytotoxic solvent, such as acetone, xylene, nitrobenzene, cyclohexanone or dimethylformamide, and dispersing the active ingredients in water using suitable surfactant emulsifying and dispersing agents.

The choice of dispersing and emulsifying agents and their amounts are dictated by the nature of the composition and the ability of the agent to facilitate dispersion of the active ingredient. It is usually desirable to use as little of this agent as possible in order not to emulsify the active ingredient after its application to the plant and not to wash it out of the plant.

Nonionic, anionic or cationic dispersing and emulsifying agents can be used, for example, condensation products of alkylene oxides with phenol and organic acids, alkylarylsulphonates, complex ether alcohols, quaternary ammonium compounds, and the like. 15 - a solid carrier such as clay, talc, bentonite, quartz, fuller's earth, and the like. In the preparation of wettable powders, the abovementioned dispersants as well as lignosulfonates may be used.

The desired amount of active ingredient can be applied per hectare of treated area in 9.36 to 1872 liters or more of liquid carrier and / or diluent, or in about 5.6 kg to 560 kg of inert solid and / or diluent carrier.

The concentration in the liquid concentrate will usually vary from about 5 to 95% by weight and in solid compositions from about 0.5 to about 90% by weight. Suitably, the sprays or dusts are applied at doses corresponding to about 0.01 kg to 112 kg of active ingredient per hectare, preferably from about 0.01 kg to 16.8 kg of active ingredient per hectare, preferably from about 0.11 to 5.6 kg. active ingredient per hectare.

The compositions of the invention may optionally contain other ingredients, such as stabilizers or other biologically active compounds, as long as they do not or do not impair the activity of the active ingredient and do not harm the plant being treated. Such other biologically active compounds include, for example, one or more insecticidal, herbicidal, fungicidal, nematocidal or acaricidal agents, plant growth regulators or other known compounds. These combinations may exert a synergistic effect.

16

The malonic acid derivatives of the formula I are preferably applied to plants under normal growth conditions. The active compounds according to the invention can be applied to growth retardation during the vegetative or reproductive growth phase.

The compounds described are useful in agriculture, horticulture and related fields and can be applied generally to gymnosperms, especially to vegetation such as woody plants and turf for slowing down the growth of these plants. The compounds of the invention are useful, for example, for regulating the height of vegetation around public roads and for slowing growth over cross sections of trees and shrubs and the like, with no adverse ecological effect.

&Quot; plants " as used herein, applies to any agricultural or horticultural plant, woody plant, ornamental plant, and racing grass. 17 -

Typical woody plants that can be treated with malonic acid derivatives of formula I include, for example, red maple, sycamore, red oak, American elm, linden, ginkgo, oak, ash, maple, fruit trees, Chinese elm, wild trees, Russian olive, maple silver, maple, oak, poplar, conifers and the like.

Other plants that may be treated with the compounds of formula I of the invention include, for example, maize, cotton, sweet potatoes, white potatoes, dough, wheat, rye, rice, barley, oats, sorghum, beans, soybean, sugar beet, sunflower, tobacco, tomatoes, canola, fruit trees, citrus, tea plant, coffee tree, olives, pineapple, cacao, banana tree, sugar cane, palm oil, herbs of the lower floor, woody shrubs, racing grasses, ornamental plants, evergreen plants, trees, flowers and the like .

The mslonic acid derivatives of the invention are effective in slowing plant growth. When used in sufficient quantity to provide a retarding effect, these compounds are very safe, do not damage and burn the plant and resist weathering, including rainwashing, ultraviolet radiation, oxidation or hydrolysis in the presence of moisture, or such decomposition, oxidation and hydrolysis that would substantially reduce the required growth retardation of the plant caused by the active ingredient or cause undesirable properties, such as phytotoxicity.

If desired, mixtures of the active compounds of the invention or combinations of these active compounds with other biologically active compounds as described above can be used.

The following non-limiting examples illustrate the invention. Example 1 Preparation of ethyl 3 - [(4-fluorophenyl) amino] -3-oxopropanoate

4.44 g (0.04 mol) of 4-fluoroaniline, 4.05 g (0.04 mol) of triethylamine and 200 ml of tetrahydrofuran as solvent are introduced into a nitrogen-flushed, air-stirred reaction flask. stirring at room temperature is rapidly added 6.02 g (0.04 mol) of ethyl malonyl chloride, which is rinsed with several milliliters of tetrahydrofuran. The temperature of the stirred mixture rose to 42 ° C and a precipitate of triethylamine hydrochloride precipitated out of the mixture.

The mixture was stirred at room temperature for about 2 hours, then the triethylamine hydrochloride was filtered off, washed with a solvent and dried to give 5.2 g (0.04 mol) of the title compound. The purple solid was dissolved in methylene chloride. The solution was washed successively with 2N HOL (3x75 mL) and water (2x75 mL), dried over magnesium sulfate, and vacuum distilled to give a crude solid.

After recrystallization from ethyl acetate / hexane followed by flash column chromatography, 3 S, 47 S (0.015 mol) of ethyl 3-C (4-fluorophenyl) amino] -3-oxopropanoate, m.p. .

Analysis for C 11 H 12 FNO 3

H, 5.37; N, 6.22. H, 5.35; N, 6.36

This compound is hereinafter referred to as Compound No. 1. Example 2

In an analogous manner to Example 1, additional compounds No. 2 to 44 were prepared, which, together with analytical data, are shown in Table A below.

Ή C Ό3 OJ OJ LT CM CM CM O O rH - * - > vo r • • • • • • • Γ • • • • • • • H H Γ H H H H H H H H H H ν νθ rH VO 0-OO σν in VO

Table ADerivatives Balloon acids of general formula

and φ

0- in ITV CM in O o o o o o o o o o o o o o o 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 —C what LTV lasts CO C— o Tt · what φ > s M VO what is 00 duration in CO CM OJ OJ rH 0) 00 in in CM σ σ OJ OJ trvν rH WHAT WHAT WHAT WHAT * * lasts for C- σ > O irv last σν O σ > VO O 00 • ν ν k k · k k k k k k k k k IT IT IT CM CM CM CM CM CM CM CM co co co co c- CO rH rH 0- CM CM CM CM uo OJ CX CO ITV Xf ITV CO 0- 0- 'φ Η- »Φ C -P Φ K > ITV O ν H H O vo vo vo vo vo vo 8 8 8 8 8 * vo vo * * * * * * * * V V ZO Z Z Z Z Z Z Z Z Z Z Z z

u 03 i T * CM CM h CM ma CM CM lt Z lt lt lt lt lt Z Z CM CM Z Z Z Z a a a CM CO ___ - / | c 1 IZ Pei rH J 1 1 rH rs o o o o o 'j · ox »k | • k 1 1 1 «k«% CO

rH K

VίCίΛίΠίΛΙΑίΛΐΛ ITV CMCMOJCMCMCMCMCMOJOJ oooooooooo I · ® XJ & CO CO oc rH * H CO c

OJ whatever

O- CD

Cv O rH rH i-I

c os —-- poo

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LÍN K co O

c 'C? ^ - * - > oo

what is VO 0Λ what M-rH o ør > CTi r r r r »1 1 1 CL) | and what VO rH rH < D C-ON CT > O rH rH

LTN RH 00 vO 00 «> I • M · CM IC - rH VO rH rH ON LTV C—« * ** «to 2S ITN 1 xt * __s VO Ό 00 • k «k oK M- Ή m xf co c NV '>> N rn irs rH O .Η H rH rn m 00 rH CO rH • k • k #k C ffl CM VO CO 00 CO \ t -J- xí " * *-ON ON ON O * * m * * * * m m m m m m m m m m m m C C C C C C C xf · H m xt · + J ® C -P a >> o θ- C * - CM vO CM o Γη rH OOO < 0 o. • k «km« k < H > s CM VO CO tr © © gt; U tf M " «W Ka ss of what

cn tu K m O 1 1 CM • h Μ rH 1 on Ι O nct * 4 hh 1 W «τ " ν om (3 ir CM 1 CM 1

I · K < CO 3 CO Q - C

03 C

CM CM C CMK CM CM C CM CM \ t

IT \ t

CM OO rH CM m - «T Μ " Μ " Μ * Μ " Example 25 Preparation of ethyl 1- (2-methyl-4,5-dichlorophenylaminocarbonyl) cyclopropanecarboxylate

5.53 g (0.03 mol) of 2-methyl-4,5-dichloroaniline, 3.18 g (0.03 mol) of triethylamine and 190 ml of tetrahydrofuran are introduced into a round bottom flask purged with nitrogen. as solvents. 5.55 g (0.03 mol) of ethyl 1-chlorocarbonylcyclopropanecarboxylate prepared as described below in Example 107 was then added in one portion with vigorous stirring. The reaction mixture was stirred at room temperature for 6 hours, whereupon the precipitated triethylamine hydrocarbon was added. the chloride is filtered off and the filtrate is evaporated in vacuo. The pale yellow solid was taken up in ether, washed with water, dried over magnesium sulfate, and the solvent was evaporated. The yellow powder was recrystallized from ethyl acetate / hexane to give ethyl 1- (2-methyl-4,5-dichlorophenylaminocarbonyl) cyclopropanecarboxylate (4.51 g, 0.01 mol), m.p. 105-107 ° C.

% C, 53.18;% H, 4.78; N, 4.43. Found: C, 53.41; H, 4.76;

This product is hereinafter referred to as compound δ. 45 26 - Example 46

In an analogous manner to Example 45, additional compounds 46 to 63 were prepared, summarized in Table B below.

Table BD Malonic acid derivatives of general formula x

CM K o

About O \ t

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O CM / O CO f rH rH 1 About CNJ CM CM O CM 1 rH rH 1 - 1 1 UO UN OOO H- (3 O c ·% 1 1 1 1 rH 1 -— H- Ή UN f > 4 O CQ H- 1 X «* • k ** 1 1 1 m 0 rH CNJ CO CNJ CNJ CM • CN • CNJ CNJ CNJ CM CM CM CM rH« U elementary analysis temperature ruptures calculated (%) found (%) (%) and 0,000 CO OC VO c - OO ON OH CM CO rH H 03 C Ή M · H- H- UN UN UN UN elemental analysis ° C) 2: oa

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VO A- OO CTV in CM 0 VO rH Ή “A- crv what A-CO 0 what PO ro m PO after PO lA

CM 00 AO CM CM AO CM AO AO LA A «A CM * A * kmm AO * A AO CM AO CM 00 AO CM CM AO CM AO rH rH LA LA A < JV O LA LA 00 VO v rH rH PO vO LA LA 00 00 thi CO e- 0 e-ca LA LT 0 o o CM o o CM • k #km #k. M «k • k o to po po o m e d e "

LA LA WHAT 00 00ν e PO e · PO PO PO POA PO POAAAAAAAAν ν PO # # # # # # # PO PO PO PO PO PO PO PO PO PO * * PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO PO 0 0 CM CM WHAT LA LA LA VO AND VO RH PO PO LA LA

r — I 0 1 LA CM CVI and 1 rH O 1 and 1 1 and 4 and CM and 4 and 1 and 1 M · 1 rH · e · 1 u 1 rH 1 PO W 4 rH O 1 1 PO K LA O CQ OO LA 0 • to 1 CM 1 CM 1 PO 1 CM 1 • to 1 PO CM CM K m CM 05

I · 03 Ο Ο 3 C0 Ο C

03 03 Μ Μ Λ 03 Μ 03 03 03 03 03 03 03 03 Μ I I I I I J J J J ML ML ML ML ML ML ML ML ML ML ML ML ML CM Ο Ο Ο Ο

• e · LA ι a 0 C0 ΙΑ CJV ΙΑ

Ο VO

ΗΗ VO OJ νο

O VO 29 - Example 64 Preparation of 3 - [(4-bromo-2-methylphenyl) amino] -3-oxopropanoic acid 6.0 g (0.02 mol) ethyl-3 - [(4-bromo-2- of methylphenyl) amino-3-oxopropanoate prepared in Example 1 (Compound No. 44) was dissolved in ca. 80 mL of ethanol and 1.2 g (0.03 mol) of sodium hydroxide in pellets was added to the solution. After stirring for 4 hours, the mixture was allowed to stand overnight, evaporated to dryness and water was added to the residue. A yellow, cloudy solution is formed which is extracted with methylene chloride and then acidified with 10% hydrochloric acid. (D <l; 1.8 g (0.01 mol) of 3 - [(4-bromo-2-methylphenyl) amino] -3-oxopropanoic acid is obtained from the white precipitate as a white solid, m.p. 163-165 ° C.

H, 3.70; N, 5.15. Found: C, 44.14; Found: C, 43.90; H, 3.68; N, 5.11.

This product is hereinafter referred to as Compound No. 64 · 30 - Example 65

In an analogous manner to Example 64, additional compounds are summarized in Table C below. Authentic Compound No. 75 was obtained from Research Services, POBox 11212, Santa Ana, California 92711. AK Mitta-la, 32/17 E. Patel Nagar, New Delhi 110 008, India. oc JU o N > £ D 3 3 3 3 3 3 3 C

1 o rH © o rH © on © 1 X Λ1 1 rH O 3 XI) o £ i > © O 1 Eh oj rH K © os 1 > s P o XD o > H 1 u © o PK

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TO

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tfV VO

VO VO r

00 VO σ > vo Ή C OJ'— HOO CO ^ * - > O rHo. υ o 35co c N 3) 'N rl < U CO rHc what what

5 (¾ Ή v- " C CM + J © nc h > © > o

c - X rH c - VO '—on ON VO 1 LP »rH tr > rH 1 “1 CTN LTV P- ir VO r rH r—! r — 1 rH vO rn cq r- P- r-1 O · * • k «0« * H- P- O m CM c CM V CM CM m #k rH rH CM • k • k # k P- P ~ CM rH n ΓΟ mm σ σ O VO VO P- P ~ rH rH «k ψ» «* • k H-

rH rH with 8 «*« »• CM CM CM CM CM trs σ > »M m» 8 »» »» »» »» »» »» »» »» »» »» »» OJ OJ OJ OJ OJ OJ OJ 0 irs m CM m 1 CM • km • x yr-V o W s «-Η • k o. CM 1 CO and H * κο O se / -N · > Oc / X X X »» »X X X X X X X X X X X X X X X X X N N N N N N N o O n Η " »R r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r CM. — Co v — — — — — — — — — — — — — — — — — — — — — — sp sp sp sp sp sp sp sp sp ΓΟ m W rH M r r 1 1 CM m «m« «« «« ow ow ow ow ow S S S S S S £ £ £ £ £ ; uu 1 1 CQ CQ ur—! I 1 CQ O Tp «3 · 1 1 m * k CM CM CM co CM m KO 1 rH H- O 1 1 r — 1 o • k | CM n merges- > o © c • hc i-i cm n p- p- p- c- > LTV VO P ~ P- 33 - Example 77 Preparation of 1- (2-methyl-4,5-dichlorophenylamino-carbonyl) -cyclopropanecarboxylic acid In a 250 ml round bottom flask, prepare a solution of 0.34 g (0.006 mol) potassium hydroxide and 0.109 g (0.006 mol) of water in 80 ml of ethanol. While cooling in an ice / sodium chloride bath to 0 ° C, a solution of ethyl 1- (2-methyl-4,5-chloro-phenylaminocarbonyl) -cyclopropanecarboxylate prepared in Example 45 in a small volume of ethanol was added and the mixture was allowed to cool. warm to room temperature with stirring for 72 hours. The resulting mixture was evaporated in vacuo to a white solid residue which was dissolved in water. The aqueous solution was extracted twice with ether, the ethereal extracts were discarded and the aqueous solution was acidified to pH 2 with 25% hydrochloric acid. The solid which separated out was taken up in ether and the acidified aqueous phase was extracted four times with ether. The combined ether extracts were dried over magnesium sulfate and evaporated in a vacuum. The white solid residue was washed with water and dried in a vacuum oven. 1.85 g (0.006 mol) of 1- (2-methyl-4,5-di-chlorophenylaminocarbonyloxycyclopropanecarboxylic acid, melting point 248 DEG-251 DEG C.) are obtained.

H, 3.85; N, 4.86. Found: C, 50.02; Found: C, 50.51; H, 4.31; N, 4.83.

This material is hereinafter referred to as Compound No. 77. Example 78

In an analogous manner to Example 77, additional compounds of the invention are prepared, summarized in Table D below.

melting C) NO O NO CM If CM O CM CM CM CM CM CM (CM 1 CM 1 CM • CM 1 CM 1 CM 1 CM 1 CM-1 1 -i- c. CM 00 O rH OJ CM i) _ > CM CM CM CM CM CM CJ CM

Tnalonic acid derivatives of formula c

X

CM X i / O CM K a & io 0 1 0 1oo

Io as

About CM NO what CM CTN NO CO NO TT ON CM CMN 00 co Z H " H " IfN ITN H CO CO NO í O If If O O N N N N N - - - - - - - - - - - - - WHAT CO CO (S c N 'gt s o o o o o o o r r r r r r r r r r r r r r r r r r r r r) IFN IfN ifN what is H " rH rH what NO If- ifN iff tf r '-r NO rH rH rH CM rH IfN o CO NO what ifN CM IfN ITN uom ns ca + j © CM what CO CO CM c -P © XJ -M- CM OO CM O ON o co 00 CM CM CM rH IfN CO ® and # »** m #k ·» ψ * · * Λ H > 00 CM CO ω rH ITN NO NO © &If;

CQ co 1 rH r-1 CM CM CM CM | 1 t — 1 r — 1 1 what LTN OO -Μ CQ c ►r * ►— · a 1 1 Ι f — iu 1 O H " IfN 'i- Ph O CQ' i- X 1 ** 1 1 l CM OJ CM CM CM '- Ί-CO I · ® XJ o α cdo c r-1 -H < ac co σ > o t > oo

CO-CO CO CO-COMBINATION-Elemental Analysis Melting Temperature No. (X) Calculated (%) Found (%) (° C) ΌC · - O LCN CM JN CO CO rHN · CM CO CM r — 1 CM in < -1 r r r ~ A m 1 O o CM CM -π λ; CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM X -μ- ξ i — 4

CM C O R O R O R O R O R O R O R O R O R O R O R O R O R O R O R O R O R O R O R O R O R O R O R O R O R O C O C O C CM O o C o C c X X X CM PO PO mm PO *. ctn rH C- o Γ— c- PO uZ ON VO c- o c - Nf ON Γ - m. N * PO ω ω CM VO rH rH X AFTER ITN LTN • · saao o If irv irv PO o ON irv IT CD 00 00 PO o VO · · *% * * # * ** rH X CM CM CM CM CM AFTER PO δ What δ v »/ ON ON C- c- C- AFTER LEN &L; LTN of rH 01 trsi

.fa (—1 h ID 03 o ¢ 3 1 U CM CM 1 I 1 Ή- 03 CM Sh 4h Í ř ř ř l l l i i i i i i i i i i i i i i i i i i i i i i i O 03 O o LÍN «« # »1 1 1 1 1 1 PO CM CM CM CM CM CM Nt PO 3,4-Cl? 48,20 3,31 5,11 48,79 3,80 5,26 220- 222, vO00 ΟΟ ο αοco ΟΛ oo

O ON

F-! HE

CM ON

PO ON

EXAMPLE 96 Preparation of ethyl 1- (4-bromo-2-methylphenyl-asinocarbonyl) -cyclobutanecarboxylate

To a nitrogen-purged reaction flask, a solution of 2.74 g (0.01 mol) of 4-bromo-2-methylaniline and 1.49 g (0.01 mol) of triethylamine in 200 ml of tetrahydrofuran were introduced. While stirring vigorously, 2.80 g (0.01 mol) of ethyl 1-chlorocarbonylcyclobutanecarboxylate prepared in Example 108 are added and the resulting mixture is stirred at room temperature for 6 hours. The precipitated triethylamine hydrochloride was filtered off, the filtrate was evaporated in vacuo and the residue was taken up in methylene chloride. The solution is washed successively with 2 times 75 ml of 2N hydrochloric acid and water, dried over magnesium sulphate and evaporated on a rotary evaporator. The crude product was chromatographed on a silica gel column using hexane / ethyl acetate (7: 3) as eluent to give 3.63 g (0.01 mol) of ethyl 1- (4-bromo-2-methyl) as eluent. phenylaminocarbonyl) cyclobutanecarboxylate as a white solid. A small sample of this product melts after recrystallization from hexane at 61-64 ° C.

For C, 52.92; C, 5.33; H, 4.12; Found: C, 52.99; H, 5.44; N, 4.05.

This product is hereinafter referred to as Compound No. 96. Example 97

In an analogous manner to Example 9o, additional compounds of the invention were prepared, summarized in Table E * below.

00 O p- 4- > WHAT CO 1 V 1 t CO T T T T o. < υ A Φ -t- > v- / O c * - rH rH ιΓν + - > P " OO CO

Malonic acid derivatives of general formula

o rH CM CM CTV rH OS 3 AAAA ro lT t o o- rH o ** " s what p- o r- P- a: r > trs OG IT ITS os N co CM CM CM CM p p p p p p p p p p p p p p p p p p p p lt lt lt lt 2 AAAA " t G rs a * s Φ Η c what CM 00 what G p- O P- p- P- © a; AAAA -3 · XJ O a >> 00 cl 00 00 > H o rH rH c CM o CM CM r * rH 1 rH rH X o CM o r t A 1 | H ITS for AAAA | CM n f CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM && Example 102 Preparation of 1- (3,5-dichloro-phenylaminocarbonyl) -cyclobutanecarboxylic acid 2.0 g (0.006 mol) of ethyl 1- (3,5-dichlorophenyl-alancarbonycyclobutanecarboxylate prepared in Example 97 (Compound No. 97) ) is hydrolyzed in the presence of 0.114 g (0.006 mol) of water and 0.355 g (0.006 mol) of ethanolic potassium hydroxide, and the resulting acid potassium salt is acidified with 25 µl of hydrochloric acid solution and worked up as described in Example 77. 0.003 mol) of 1- (3,5-dichloro-phenylaminocarbonyloxycyclobutanecarboxylic acid as a beige colored solid, m.p. 159-160 ° C (Compound No. 102).

Calc'd for C 12 H 11 O 2 N 3: 50.2% C, 3.85H, 4.86N; Found: C, 50.20; H, 3.83; H, 4.34;

In an analogous manner to that described in Example 102, the other compounds of the invention are prepared as summarized in Table F below.

J on Η J IT V V H H H H H H H H H H H H H H H H H X X X X X X lt lt lt (ir V V (((((((((((((((((((((((((((((( 03 N 03 · 'rH ω < M 04 av 03 00 C J 04 CT and C «« · * N o O and VO lf lf l < sc 03 Ή cum Ό3 of · * 1 1 1 c 03 Λ s 03 rH O OJ tr 03 c H what what-03 K * · »« km on on O & P > 00 04 OJ r — i > K «ko r O O f f f f f f f f f f f f f f f f f f f c c c c c c o o o o o Example 107 Preparation of ethyl-1-chlorocarbonylcyclopropanecarboxylate for stirred-up. a 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 are added dropwise while cooling to 0 ° C. 50.0 g (0.27 mol) of diethyl The reaction mixture was stirred at room temperature for about 16 hours and then the solvent was evaporated under reduced pressure. in water, the aqueous solution was first extracted with ether, then with 25% aqueous hydrochloric acid to pH 2 and the resulting aqueous suspension, the resulting organic acid is extracted four times with 400 ml ethyl ether.

The ether extract was dried over magnesium sulfate and evaporated in vacuo to give the corresponding monocarboxylic acid as a clear liquid residue. The clear liquid material was dissolved in 300 ml of methylene chloride, 74 g (0.62 mol) of thionyl chloride were added to the solution, and the reaction mixture was refluxed for about 16 hours.

After evaporation of the volatiles under reduced pressure, 45.7 g (0.25 mol) of ethyl 1-chlorocarbonylcyclopropanecarboxylate are obtained.

NMR (CDCl3, .delta. In ppm): 1.22-1.50 (t, 3H), 1.75 (s, 4H), 4.1-4.52 (q, 2H). - 43 -

This product is hereinafter referred to as Compound No. 107. Example 108 Preparation of ethyl-1-chlorocarbonylcyclobutanecarboxylate 20.0 g (0.10 mol) of diethyl 1,1-cyclobutane dicarboxylate are saponified 6.59 g (0.10 mol) potassium hydroxide in a mixture of 200 ml of ethanol and 1.80 g (0.10 mol) of water. After work-up, the monocarboxylic acid formed was reacted with 8.86 g (0.07 mol) of thionyl chloride dissolved in methylene chloride as described in Example 107. The reaction was carried out with the aid of the procedure described in Example 107.

After evaporation of the solvent, 7.48 g (0.04 mol) of ethyl 1-chlorocarbonylcyclobutanecarboxylate are obtained. NMR (CDCl 3, ppm) δ 1.10-1.44 (t, 3H), 1.7-2.85 (m, 6H), 4.05-4.5 (q, 2H).

This product is hereinafter referred to as Compound No. 108. Example 109 Preparation of ethyl 3-C (4-chlorophenyl) amino-1,3-oxopropanate

Using the procedure described by A · K. Sen and P. Sengupta in Jour. Indian Chem. Soc. 46 (9), 857-859-44 (1969), 25.4 g (0.20 mol) of 4-chloroaniline are reacted with 48 g (0.30 mol) of diethyl maionate. This reaction yields a greenish-colored solid which, after recrystallization from equal parts of toluene and hexane and then from isopropyl ether, yields 9.0 g (0.04 mol) of ethyl-3-C (4-chlorophenyl) amino-1-3- oxopropanoate as white crystals, m.p. 82-83 ° C.

% C, 54.67; H, 5.01; H, 5.80; C, 54.90; H, 4.94; N, 6.07.

This product is hereinafter referred to as Combination No. 109. Example 110 Preparation of 1- (4-Bromo-2-methyl-phenylaminocarbonyl) -cyclobutane-carboxylic acid 3.0 g (0.009 mol) ethyl 1- (4-bromo-2-methylphenyl) -minocarbonyl) cyclobutanecarboxylate prepared in Example 96 (Compound No. 96) is hydrolyzed in an analogous manner to Example 102. 2.19 g (0.007 mol) of 1- (4-chloro-2-methylphenylaminocarbonyl) cyclobutanecarboxylic acid (compound m.p. 154-155 ° C. EXAMPLE 111 Effect of Typical Malonic Acid Derivatives on Retarding Bean and Wheat Growth

Solutions of the test compounds listed below in Table G were prepared by dissolving 68.8 mg of the respective compound in 5.5 ml of acetone and then making up to a final volume of 11.0 ml with water. If the solution became turbid when water was added, the addition of water was stopped and acetone was added to a total volume of 11.0 ml. The resulting stock solutions contained 6,225 parts by weight of the respective compound per million parts by weight of the solution. Test concentrations in test compound parts per million parts by weight of the total solution used in the growth retardation tests in Table G were obtained by appropriate dilutions of the stock suspension with a mixture of equal volumes of acetone and water.

Seeds of beans, wheat, cucumber, sunflower, flax, buckwheat, tomato, rye, marigold, soybean, chicken legs, oats, and peas were planted in sandy loam soil in flat trays with the following dimensions: 8.9 cm x 20 cm. , 1 cm in length x 2.54 cm in height. 12-14 days after sowing, at a time when the first triple leaf bean tulle was at least 3 cm long, each concentration of test compounds listed in Table G was applied to one to 46-leaf-spraying tray using a spraying device 68 , 6 kPa (all areas were sprayed with an amount corresponding to 4.48 kg / ha).

As a control, an aqueous acetone solution containing no test compound was sprayed onto the test dish. After drying, all plant trays were placed in a greenhouse at 26.7 ° C + 2.7 ° C and 50% ± 5% humidity. Growth retardation was determined visually and recorded 10 to 14 days after treatment.

Visual evaluation of growth retardation was recorded using a numerical scale from 0 to 10, indicating the degree of growth retardation compared to untreated control. An O value indicates no visible response, a value of 5 indicates a 50% growth retardation compared to a control, and a value of 10 is a 100% growth retardation compared to a control. In other words, the value of 5 indicates that the plant growth is only half that of the control plant, or that the plant grows at a rate that is half that of the control plant. This evaluation system indicates any reduction in plant height compared to an untreated control plant. The results are shown in Table G and show that treatment of plants with certain malonic acid-derived compounds causes a significant growth retardation compared to untreated control plants. - 47 -

Table G (1) é Effect of typical malonic acid-derived compounds ns Bean growth retardation Compound No. Control growth retardation 0 1 2 2 7 6 2 7 7 9 2 10 2 11 4 14 1 16 2 17 6 18 9 21 6 22 4 22a 6 23 2 24 8 25 2 26 5 48 - growth retardation value Compound No. 27 5 28 3 30 2 31 2 32 9 33 3 34 3 37 4 39 5 40 2 41 2 43 2 44 6 46 2 47 5 48 2 49 2 50 3 51 2 52 4 53 2 54 2 55 2 56 3 49 - Compound δ. growth retardation value 58 2 60 4 62 2 65 3 66 4 67 3 68 2 69 7 71 2 72 3 74 3 75 2 77 4 78 9 79 3 81 4 82 3 83 7 84 2 85 2 87 2 88 4 89 4 90 3 50 - 50 - Compound No. Value Growth Improvement 92 5 93 4 95 2 96 5 102 3 109 4 51 -

Table G (2) Effect of typical malonic acid compounds on wheat growth retardation Compound No. growth retardation control 0 18 1 32 2 41 3 50 2 52 2 56 2 60 3 74 2 77 2 78 3 81 4 82 5 83 2 84 2 88 2 89 2 90 2 - 52 - - 52 - Compound δ. growth retardation value 92 2 93 2 96 2 Example 112 Effect of representative malonic acid derivatives on wheat growth retardation

Tests of the test compounds listed in Table H below are prepared by dissolving the respective compounds in a mixture of equal volumes of acetone and water containing 0.05% (v / v) Triton X-100 surfactant (Bohm and Haas Company, Philadelphia, Pennsylvania). As described below, these solutions of the test substances are applied to the wheat in an amount corresponding to 0.56 kg / ha or 1.12 kg / ha.

Wheat seeds are sewn into sandy loam soil contained in 8.9 cm wide, 20.1 cm deep, 2.54 cm tall dishes. 8 days after emergence, when the wheat plants are in the 2 to 3 leaf growth stage, each dish is treated with an appropriately concentrated test substance solution. Spraying is carried out on a sheet, using a spraying device operating at a pressure of 53-68.6 kPa (all trays are sprayed with a volume corresponding to an application of 1123 liters of spray per hectare).

As a control, aqueous acetone solutions containing no test compound are used. After drying, all the wheat-treated plates are placed in a greenhouse at 26.7 + 2.7 ° C and 50 + 5 2a moisture and visually delayed growth 14 days after treatment.

The observed growth retardation is evaluated as a percentage, compared to that found in the untreated control. An O i value means no visible response, a 50% value means that wheat plant increments are half with wheat increments in untreated dishes and 100% is the maximum response.

This evaluation system indicates any retardation of wheat growth compared to an untreated control experiment. The results of this experiment are shown in the following Table H and show that the treatment of wheat plants with representative malonic acid derivatives according to the invention results in a significant reduction in wheat growth compared to untreated control plants. 54 -

Table Η Effect of typical malonic acid compounds on wheat growth retardation Compound dose growth inhibition No. kg / ha in percent control 0 63 0.56 30 1.12 40 78 0.56 60 1.12 70 81 0.56 20 1 , 12 30 50 0.56 10 1.12 10 82 0.56 30 1.12 40 83 0.56 40 1.12 70 84 0.56 50 1.12 60 - 55 - Example 113 Effect of representative malonic acid derivatives on slowing down the growth of red and western sycamore

The solutions of the test compounds listed in Table I below are prepared by dissolving the respective compounds in a mixture of equal volumes of acetone and water containing 0.1% (v / v) Triton X-100 surfactant (Rohm and Haas Company, Philadelphia). , Pennsylvania). As shown below, these solutions of test substances are applied to red maple and western sycamore at a rate of 1.12, 2.24 or 4.48 kg of active ingredient per hectare.

The purchased red maple seedlings (Acer rubrum) and Western sycamore or sycamore (Platanus occidentalis) are grown in about four liter plastic pots containing sandy loam soil. The seedlings are grown in a greenhouse with a temperature of 26.7 f 2.7 ° C and a humidity of 50 + 5 5c. After one month, the trees are cleared of buds, leaving only one major shoot 10 to 15 cm long. At this time, sprays were applied to the individual trees by spraying on a leaf using a spraying device operating at a pressure of 68.6 kPa at various concentrations (all trees were sprayed with a volume corresponding to the application of 1123 liters of spray per hectare). 56 -

As control 3e they use mixtures of water and acetone containing no test compound to spray control trees. After drying, all the trees return to the greenhouse for one month. One month after treatment, growth retardation is then detected and recorded in individual cases. For each tree, the length of the shoots is measured, which is compared to that of the untreated control trees, which shows the percentage of growth inhibition of the shoots. The average length of shoots for untreated control trees is 48 cm for red maple and 53 cm for western sycamore. The results shown in Table I below represent the average of three experiments. The results shown in Table I show that significant growth retardation is observed when treating seedlings of red maple and western plane with certain malonic acid derivatives of the invention compared to untreated control plants.

57 - Table I Effect of Typical Retardation of Compounds Derived from Balon Acid Derivatives of Red Maple Tree and Plane Degradation Percentage Compound. control 63 dose kg / ha maple Red western sycamore O o 1.12 34 15 2.24 40 16 4.43 43 20 1.12 76 77 2.24 97 84 4.48 97 88 73 58 - Example 114 Effect of representative malonic acid derivatives on slowing red maple growth Western Plane z)

The compounds of the test compounds listed in Table J below are prepared by dissolving the respective compounds in a mixture of equal volumes of acetone and water containing 0.1% (v / v) Triton X-100 surfactant (Rohm and Haas Company, Philadelphia). , Pennsylvania). As described below, these solutions of test substances are applied to Red Maple and Western Plane in a dose equivalent to 1.12 and 2.24 kg of active ingredient per hectare.

The purchased red maple seedlings (Acer rubrum) and Western sycamore or sycamore (Platanus occidentalis) are grown in about four liter plastic pots containing sandy loam soil. Seedlings are grown in a greenhouse with a temperature of 26.7 + 2.7 ° C and a humidity of 50 + 5%.

After three months, the trees are cut to half height and, after 24 hours of trimming, the test trees are sprayed onto the individual trees by spraying on a leaf using a 68.6 kPa pressure spraying device (all trees are sprayed with a volume corresponding to the application). 1123 liters of spray per hectare). 59 -

As a control, mixtures of water and acetone containing no test compound are used to spray control trees. After drying, all trees return to the greenhouse for 45 days. After these 45 days, growth retardation in individual cases is detected and recorded. Evaluation is done visually.

The growth of shoots in each tree is visually determined and compared to that of the untreated control tree, and this comparison is expressed as growth retardation in percent. 0% means no visible response, 50% means that the increment of the treated tree is only half that of the control tree or that the treated tree grew at half the rate of the control tree, and 100% represents the maximum response. This evaluation system indicates any growth retardation compared to the untreated control. The results shown in Table J below represent the average of three replicates. The results shown in Table J show that in the treatment of Red and Western Plane maple with certain malonic acid derivatives of the invention, there is a marked retardation of increment compared to the control plants treated. 60 -

Table J 0 Effect of typical compounds derived from maionic acid on the growth retardation of maple red and western olate slowing growth in percent compound no dose kg / ha red maple sycamore western control - 0 0 63 1.12 47 8 2.24 42 9 78 1 , 12 85 43 2.24 91 46

Claims

-61- ¥ 1 / PATENT CLAIMS 1. For this purpose, the formula I for the growth retarding of plants, comprising a compound of the general formula I in which

R 1 and Y 1, R X 2 n is hydrogen or C 1 -C 3 alkyl, are each hydrogen or together with the adjacent carbon atom form a cyclopropane or cyclobutane group, is oxygen or NH, is halogen, trifluoromethyl or methyl and is 0, 1, 2 or 3, provided that when n is greater than 1, the substituents X are the same or different

2. A composition according to claim 1 wherein the active compound is a compound of Formula 62

3. The composition as active ingredient according to claim 1, comprising the compound of the formula by

like

4. The formulation according to item 1, the active ingredient labeled, comprises the compound of formula by the fact that CH 3 CH 2 -

formula

5. A composition according to claim 1 wherein the active ingredient is compound 63

N <

6. The composition according to claim 1, wherein the active compound is a compound of formula (V7) - HO - C - 1 0 1 0 1 NH - () - Br »f rt

7. A composition according to claim 1 wherein the active compound is a compound of formula

8. The composition as active ingredient according to clause 1, comprises a compound of formula (n) and formula (e) by 64 as

9. The composition of claim 1, wherein the active agent is a compound of formula IIa

Cl ch3ch2 - 0 - C - V - C -

10. A composition according to claim 1 wherein the active compound is a compound of formula (I)

11. The composition of item 1, wherein the active agent is a compound of the formula: EMI2.0 [0031] by 65 [mu] CH3 CH2

12. The composition of item 1 as active ingredient comprises 1, wherein the compound of formula (t) is defined

13. The composition of item 1 as active ingredient comprises 1, wherein the compound of formula (t) is defined

66

14. A composition according to claim 1 wherein the active compound is a compound of Formula 66

* ♦

15. Composition according to claim 1, characterized in that it contains as active substance a compound of formula CH3CH2 - o o IVc - CH2 by 1%.

2? is Z? *? * / - you