DD264372A5 - PROCESS FOR DELETING PLANT GROWTH - Google Patents

Abstract

The invention relates to a method for delaying plant growth. According to the invention, an effective amount of a compound of the formula ## STR3 ## which is sufficient for delaying plant growth, is applied to the plant, in which, for example, R 1 and R 2 independently of one another represent an optionally substituted carbocyclic or heterocyclic ring system and the like. al .; Y1 and Y2 independently of one another an optionally substituted heteroatom; Y3 and Y4 are each independently hydrogen, an optionally substituted heteroatom or a substituted carbon atom, an optionally substituted branched or straight chain having two or more carbon atoms or heteroatoms in any combination, halogen, alkylcarbonyl, formyl and. al .; Y5 and Y6 independently of each other oxygen or sulfur. formula

Description

The inventive method is used in horticulture and agriculture.

Characteristic of the known state of the art

Certain ІІаіопзаиге derivative compounds have been known in the art for some time. See, for example, US Pat. No. 2,504 and US Pat. No. 3,254,108. Some blalonic acid derivative compounds have been described in the art to induce certain plant growth-regulating reactions such as fruit prevention 3, rooting of cuttings and the formation of parthenogenetic fruits ·

US Pat. No. 3,072,473 discloses U-arylmalonicinic acids and their esters and salts, IT, N'-diarylmalonamides, Ы-alkyl-IT-arylmalonamide acids and their esters and salts, and N, N'-dialkyl-1! T, H * diarylmalonamides which may be useful as plant growth regulators and herbicides. JA-PS 34 39 803 (1984) describes halonic acid anilide derivative compounds which may be useful as plant growth regulators. The plant growth-regulating properties of substituted malonyl monoanilides are described by Shindo, Έ. and Kato, II., Lleiji Daigaku Uoogaku-bu-Kenkyu Hokoku, Vol. 63, pp. 41-58 (1984).

Certain malonic acid derivative compounds and the use of malonic acid derivative compounds to retard the plant

however, the following description has not yet been published in the art.

Object of the invention

The aim of the invention is to provide a novel method for retarding plant growth.

Explanation of the essence of the invention

The object of the invention is to use novel uronic acid derivative compounds for delaying plant growth.

A further object of the invention is to find novel malonic acid derivative compounds having the desired properties and to provide processes for their preparation. These and other objects will become apparent to those skilled in the art from the discussion herein.

The object of the invention is achieved by a method for retarding the growth of plants, which consists in that sufficient to delay plant growth v / effective amount of a compound of formula

\ C / G - Il ^Υ 2 -R ₂ σ - Il - 4 V

(1)

wherein ß-, Rp, Y- »» Υ «» Υ <5 »Υλ» Yc u * ¹⁰ · Yg c & ^{e have} later defined meanings applied to the plant.

The invention also relates to novel malonic acid derivative compounds and to methods for the preparation of these compounds.

^T .7ie highlighted above, the invention relates to a method for retarding plant growth by use of certain Malonsäurederivatverbindungen. In particular, the invention includes a method of retarding plant growth, which comprises applying to the plant an effective amount of a compound of the following formula sufficient to retard plant growth

^Y 5

in which:

R-. and R ₂ are independently a substituted or unsubstituted, carbocyclic or heterocyclic ring system.

which has been selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridging ring system which may be saturated or unsaturated, the permissible substituents (Z) being the same or different and being one or more of hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, formyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy,

Formamidino, alkylsulfone "

amido, oialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl. Hydroxy, amino, azido, azo, aminocarbonyl, alkylaminocarbonyl, hydrazino, oialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, oialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino wherein the permissible substituents are the same or different and are: one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; Alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy. Alkenyl, polyhaloalkenyl, alkenyloxy,

Alkynyl, alkynyloxy, polyhalogenoalkenyloxy, polyhaloalkyryl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, oi- or polysaccharide, haloalkyl , Haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, isocyano, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl , Aminosulfonyl, alkylaninosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, polyhalogenacyloxy, aroy loxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, halo-asulfonamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl (alkyl) amino, aralkylamines, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl , Dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, diazo, alkylidene, alkylimino, hydrazono, semicarbazones, dialkylsulphonium, dialkylsulphanylidene, dialkyloxosulphanylidene, -Χ, βX, -XR ·, X-R ™,

^Υ 7 ^Υ 7

II ⁷ II ⁷

-χ - R ₃ . - P- Y ₈ R ₄ . - Y ₁₀ - P

^Y 9 ^R 5

^ ^Y 8 ^R 4

; or

R ₁ and R- are independently hydrogen or derivative salts or a substituted heteroatom or a substituted carbon atom or a substituted or unsubstituted, branched or straight chain having two or more carbon atoms or heteroatoms in any combination, where the permissible substituents Z are as hereinbefore defined ;

Y. and Y ₂ are independently a substituted or unsubstituted heteroatom in which the permissible substituents are Z having the above meaning;

Y, and Y ^ are independently hydrogen or a substituted or unsubstituted heteroatom or a substituted carbon atom or a substituted or unsubstituted, branched or straight chain having two or more carbon atoms or heteroatoms in any combination, or halogen, alkylcarbonyl, formyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, Alkoxycarbonylalcylthio, polyhaloalkenylthio, thiocyano, propargylthio, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino * alkylsulfamido, dialkylsulfamido,

Alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, hydrazino, azo, aminocarbonyl, alkylaminocarbonyl, azido, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano * hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino, wherein the permissible substituents are the same or different and represent one or two of propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; Alkylthio, polyhalogenoalkylthio, alkylsulfinyl, Polyhalogenalkylsulfinyl, alkylsulfonyl, PoIyhalogenalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, Polyhalogenalkylsulfonylamino, Polyhalogenalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, Polyhalogenalkenyl, alkenyloxy, alkynyl, alkynyloxy, Polyhalogenoalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkane oil, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, Alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfo nyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, isocyano, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhalogeno

acyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, Halogenacyloxy, Polyhalogenacyloxy, aroyloxy, alkylsulfonyloxy * Alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, Polyhalogenalkylsulfonyloxy, aroylamino, Halogenacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanates isothiocyano , Cycloalkylamino, trialkylammonium, arylamino, aryl (alkyl) amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamines, alkoxyaraino, aryloxyamino,

-A, "» AK ₃ ,

Y ₇ Y ₇

II ⁷ II ⁷

^{л K} 3 ' ^v 8 4 »10 8 4

X \

Y ₉ R ₅ Y ₉ R ₅

^Y 8 ^R 4

Y ₉ R ₅

wherein the permissible substituents Z are as defined above; or

Y ₃ and Y _{4 taken} together are oxo, thiono, diazo, * "X or sX-R ^, or substituted or unsubstituted alkylidene, alkylimino, hydrazono, oialkylsulfuranylidene, dialkyloxoulyl

-furanylidene. Semicarbazones, hydroxyimino, alkoxyimino or aryloxyimino, wherein the permissible substituents Z are as defined above;

Y, and Ѵd may be linked together to a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which is saturated or may be unsaturated, wherein the permissible substituents Z are as defined above; and

Y ₅ and Y ₆ are independently oxygen or sulfur; where:

X is a covalent single or double bond, a substituted or unsubstituted heteroatom or substituted carbon atom, or a substituted or unsubstituted, branched or straight chain having two or more carbon atoms or heteroatoms in any combination, the permissible substituents Z being as hereinbefore defined ;

R ₃ is a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridging ring system which may be saturated or unsaturated, wherein permissible subsi-

are tentants Z with the meaning explained above; or

R- is a substituted heteroatom or substituted carbon atom or a substituted or unsubstituted, branched or straight chain having two or more carbon atoms or heteroatoms in any combination wherein the permissible substituents Z are as hereinbefore defined;

^Y 8 ^R 4

Y ₉ R ₅

The alkyl-containing components in Formula 1 may contain between about 1 and about 100 carbon atoms or more, preferably between about 1 and about 30 carbon atoms, and most preferably about 1 to about 20 carbon atoms. The polysaccharide component may contain up to about 50 carbon atoms It is believed that all compounds covered by formula JL are those compounds which have no unfilled binding positions. With respect to the malonic acid derivative compounds of the present invention, it is best that when both Y ₁ and Y _{2 are} -NH-, then R ₁ and R _{2 are} independently components other than hydrogen, alkyl or aryl are ·

According to the invention, hydrogen or derivative salts refer to hydrogen or any suitable derivative salt substituents, which may therefore be substituted. For explanation, oerivate salt substituents are, for example, ammonium, alkylammonium, polyalkylammonium, hydroxyalkylammonium, poly (hydroxy

alkyl) ammonium. Alkali metals, alkaline earth metals and the like,. including their mixtures «

The monocyclic ring systems included by R ₁ , R ₂ and R ₃ in formula 1 can be represented by the generalized formula 2 as follows:

V- "

wherein B _{1 is} a saturated or unsaturated carbon atom and A _{1 is} a ring-forming atomic chain which, together with B, forms a ring system with 0 to 3 double bonds or 0 to 2 triple bonds. A ₁ may contain only 2 to 12 carbon atoms Contain 1 to 11 carbon atoms and from 1 to 4 heteroatoms, which may be independently selected from N, O, S, P or other heteroatoms, or may contain only 4 ring-forming heteroatoms ·

Monocyclic ring systems represented by Y ₃ and Υ., Which are linked together in formula I 1 , can be any monocyclic ring system of R ₁ , R and R ₃ correspondingly positioned in formula 1 .

Ring-forming heteroatoms can attach oxygen atoms in some cases, such as. B, in aromatic N-oxides and ring systems containing sulfinyl, sulfonyl, selenium oxide and phosphine oxide components.

Selected carbon atoms contained in cyclic compounds formed by B ^ and A containing at least 3 ring-forming atoms can attach carbonyl, thiocarbonyl, substituted or unsubstituted imino groups or substituted or unsubstituted methylidene groups represents one or more substituents independently selected from the group of substituents defined for Z in the preceding (a).

The bicyclic ring systems represented by R ₁ , R ₂ and R ₃ in formula 1 can be represented as follows by the generalized formulas _3 and 4:

A-

wherein Bp and B _{3 may} independently be a saturated or unsaturated carbon atom or a saturated nitrogen atom, Ap and A _{3 are} independently the ring-forming atom chains described below and Z represents one or more substituents independently of the group defined for Z above The combination of A ₂ and A ₃ in combination with Bp or B ₃ may contain from 0 to 5 double bonds. A ₂ and A, independently of B ₂ and B ₃ , may contain only 1 to 11 carbon atoms, may contain a combination of 1 to 3 heteroatoms which are independently N, O, S, P or other heteroatoms.

are selected together with 1 to 10 carbon atoms or may contain 1 to 3 ring-forming heteroatoms alone ·

Ring-forming heteroatoms can in some cases attach oxygen atoms, such as ring systems included in the aromatic N-oxides and the sulfinyl, sulfonyl, selenium oxide and phosphine oxide groups. Selected carbon atoms contained in A ₂ and A can attach carbonyl, thiocarbonyl, substituted or unsubstituted imino groups or substituted or unsubstituted methylidene groups.

Bicyclic ring systems represented by Y and Y ₄ , which are linked together in formula 1 , can be any of the bicyclic ring systems of R 1, R "and R z correspondingly positioned in formula 1 .

With respect to the structures covered by formulas Ъ and 4, the following is noted:

(a) If B ₂ and B _{3 are} both nitrogens, groups A ₂ and A must contain not less than three ring atoms each;

(b) If В », but not B_, is nitrogen, then either A ₂ or A ₃ must contain at least three ring atoms and the other group must contain at least two ring atoms;

(c) If one of the groups A "or A _{3 contains} less than three ring atoms, the other group must contain at least three ring atoms and the bridgehead atoms must be saturated.

d) When the group A ₂ or A contains a carbon atom bearing a carbonyl, thiocarbonyl, imino or methylidene group, it must together with B ₂ and B _{3 form} a cyclic compound having at least four members ·

(e) When an annular double bond to one of the two rings shown in Structural Formulas J5 and 4 is exocyclic, it must be contained in a ring of at least five members and must be exocyclic to a ring of at least five members, and

(f) When a group A ₂ or A _{3 is} connected by 2 double bonds to the bridgehead B ₂ and B ₃ atoms, it is understood that the group A ₂ or A ₃ contains a double bond and the bridgehead atoms are considered unsaturated.

It is understood that the bicyclic ring systems defined for the interconnected R ₁ , R ₂ , R ₃ and Y, and Y ₄ may be spirocyclic ring systems and are not limited to the fused bicyclic structures of formulas Ъ and ₄ Spirocyclic ring systems may be saturated or unsaturated, carbocyclic or heterocyclic compounds and may be substituted independently by one or more substituents Z as defined above.

Polycyclic ring systems, that is greater than 2 rings, by

"l * ^ 2 ^{un <*"} are detected ^{in Forme} JL ^ 3, can follow by the generalized formulas 5, 6, 7 and Q are presented:

wherein B ₄ , B ₅₁ Bg and B _{7 may} independently be a saturated or unsaturated carbon atom or a saturated nitrogen atom, and A ₄ , A ₅ , Ag and A _{7 are} independently ring-forming atomic chains which together with one (but not both) of them associated bridgehead atoms may contain from 0 to 2 double bonds. "The Z groups represent one or more substituents independently selected from the group of substituents defined for Z above."

The ring-forming elements of A ₄ , A ₅ , Ag and A ₇ may independently of B ₄ , B ₅ , Bg and B ₇ contain 1 to 11 carbon atoms, they may contain a combination of 1 to 10 carbon atoms and from 1 to 3 heteroatoms, which are independently selected from N, O, S, P or other heteroatoms, or may contain from 1 to 3 heteroatoms alone. Ring-forming heteroatoms may in some cases attach oxygen atoms, such as in aromatic N-oxides and the sulfinyl, sulfonyl "Selenium Oxide and Phosphine Oxide Group-containing Ring Systems" The group Ag may be sometimes defined as a bond "Selected carbon atoms contained in A ₄ , A ₅ , Ag, and A ₇ may attach one or more carbonyl, thiocarbonyl, or substituted or unsubstituted imino groups.

In Structural Formula j3, the group B ₃₁ B _g and B _{10 are} independently a saturated or unsaturated carbon atom or a saturated nitrogen atom. "The group B ₁₁ may represent a saturated or unsaturated carbon atom or a nitrogen or a phosphorus atom" The groups A ₃₁ A _g and A ₁₀ represent ring-forming atom chains, which together with 1 from the groups Bg, Bg, B _10, and B ₁₁ can contain 0 to 2 double bonds. «

Qie ring-forming elements of groups A ₈ , A ₉ and A ₁₀ may independently of the groups Bg, B _g , B ₁₀ and B contain from ₁₁ to 10 carbon atoms, may contain 1 to 10 carbon atoms in combination with 1 to 3 heteroatoms, which are independent may contain from 2 to 3 heteroatoms alone. Ring-forming heteroatoms may, in some cases, attach oxygen atoms such as, for example, in the aromatic N-oxides and in the sulfinyl, sulfonyl, and N, O, S, P or other heteroatoms. Selenium oxide and phosphine oxide group-containing ring systems · Selected carbon atoms contained in the groups Ag, Ag and A ₁₀ can attach one or more carbonyl, thiocarbonyl or substituted or unsubstituted imino groups ·

It is understood that the polycyclic ring systems defined for the interlinked R ₁ , R ₂ * R ₃ and Y ₃ and Y may be spirocyclic ring systems and not the fused polycyclic structures of the formulas j>, 6, J7 and Q are limited · spiro cyclic ring systems may be saturated or unsaturated, carbocyclic or heterocyclic, and may independently by one or more of the substituents defined in the preceding for Z may be substituted ·

By Y ₃ and Y _4, which are linked in formula _1 with each other, as shown polycyclic ring systems may each correspondingly positioned in formula JL polycyclic ring system of R _1, R ₂ and R ₃ may be ·

The bridged bicyclic structures encompassed by R ₁ , R ₂ and R ₃ in Formula 1 can be represented by the generalized formulas _9, _10 and JLl as follows:

^v ll Z ² Z

wherein B ₁₂ and B _{13 may} independently be a saturated carbon atom optionally substituted by Z or a nitrogen atom, and the groups A ₁₁ , A ₁₂ and A _{13 are} independently ring-forming atomic chains independently of B ₁₂ and B ₁₃ 0 to 2 The groups Z represent one or more substituents that have been independently selected from the group of substituents defined above for Z (n).

The ring-forming elements of A ₁₁ , A ₁₂ and A ₁₃ , independently of B ₁₂ and B ₁₃ , may contain only 1 to 11 carbon atoms, may contain a combination of 1 to 10 carbon atoms and 1 to 3 heteroatoms independently under N, O, S , P or other heteroatoms, or may contain 1 to 3 heteroatoms alone, provided that when one of the groups A ₁₁ , A ₁₂ and A _{13 is} a single heteroatom, the other two groups must contain two or more ring-forming atoms. A second requirement is that when either or both of B ₁₂ and B _{13 are} nitrogen, groups A ₁₁ , A ₁₀ and A ₁ must contain at least two saturated ring-forming atoms.

Ring-forming heteroatoms can in some cases attach oxygen atoms, as for example in the sulfinyl, sulfonyl, selenium oxide and phosphine oxide components. In A ₁₁ , A ₁₀ and A ₁

selected carbon atoms can attach one or more carbonyl, thiocarbonyl or substituted or unsubstituted imino groups.

Bridged bicyclic structures represented by Y, and Y., which are linked together in formula 1 , can be any bicyclic bridge system of R ₁ , R _2, and R positioned in formula _1 «

It will be readily apparent that Formula 1 covers a wide variety of malonic acid derivative compounds. Illustrative malonic acid derivative compounds within the scope of Formula 1 that can be used to retard plant growth are listed in Tables 1 through 11 below.

Table 1 Representative malonic acid derivative compounds

RV

3-f- ' 3-f-i J-f) 3-F " J-f · 3 Cf J-Cf] J-Cf ^ J-Cf] 3-Cf] 3-f-i 3-r- 3-f- J-f- < J-I - < 3-f - < 2-f- ( 2-f · < г-г- г-f- ' k-CI k-CI ►-C1 »• r i- "r , -S-Cl -5-G1 -S "r i- "r -S-ir Cl ICI ICI  ir l-lr I ir I.I-CLJ IJ-Cl ₂ I CM-Ir l-CI-5-lr

ХД

он

"ONM

т] он

OK OH

OH

X ₂ H

OH KH,

D-I5328 3542V / 9463V

Table 1 (Forts)

о о

R 1 -C-CH ₂ -C ¹ -NH-

R ¹ .

₇ .f-4-if - »- C)

OCjHj

OH

0-15328 3542V / 9463V

UH

2. «ifj-Sf i.4» r ₂ if Mr- * Cl-Sf

CH, -

г-CH ₃ -

4-Cl-S-f

4-Cl-S-r

4-ar-s-r

4- »r-S-f 4ir-S, f

OCH ₃

0 - C ₃ H ₁

OH

OCH, OH 0СД

OH

"л

ON "

OH

0 - .. СД

OK

Table 1 (Forts)

R *.

28 / 9463Ѵ

2-Cl-4-CF β! - «jO-« ir ί-CM -4-Cf Cf O-

г-с »-« - ι

осд

"И.

! - "Г-4-С1

Table 2 Representative malonic acid derivative compounds

Z \

ОСИ KH j

KH CH ₂ SCH ₃ KH ₂ CN ₂ SO ₂ CH ₃

KH ₂ CH ₂ SO ₂ CH ₃

KH ₂ CCH ₃

2СИ _зТ «

г f 4 | · γ з. «- с,

Cl

-f i-Or

-CH ₃ 4-Br

-CN -4Br-S-Cl

0-15328 3S42V / 9463V

24 Table 2 (Forts)

R'g-w- · ₂

pi 7 ·

^R 8 ^Z 9

KH ₂ CHIf ^^

KN ₂ COMl ₇

0-15328 3542V / 9463V

Z. "С"

2-CHj-4-ir 4-lr

4 cl

OH.C (CHj) ₂ ^J · ***

/ " ¹ J 2 4- (

"^ SCH,

KH-CH.HNce си ^г CH ₃ -4 · er

7 y a rl

KH ₂ CH ₂ OC-WIC ₂ H) * O

KH ₇ , '' - '"' - ⁰ J

3.4 Cl ₂

KH,

3,4 (Cf ₁

25 Table 2 (Forts)

0-15328 3542V / 9463V

K ₂ Hj

3-or-S-Cl

3 Cl-S-CF

jj 2 2 3-Ir-S-CF ₃ KH CH SO CH CH ОН 3-F-4-Or KHjC ·· 4-1 KH CH С. « г.4-сі _г 0-C (CN -) С "Н. 4 cl KH СИ KH 3 F-S-Cl KHjCO ₂ C ₂ Hj 3 F-4-CI OCHjCHjlQ J-F-4.S-CI j KH (CH) СН SC И г-Г-4-CI-S-lr ки ₂ ски ₃ ? F-4-Ir-S-CI 0-И <С (СИ) -С0 С И ? .4 CIj-S-F O-CN $ · HN 2 Cl-4-Or-S-F С · в- Си SS ЯИСИ ?, 4-Lrj-S F 2 Ir 4 Cl-S-F S-CH CH SCHj 7 CH 4 CI-S- ( S-CHCOCH ₁ 2 СИ 4-Ir-Sf

Table 2 (cont.)

R'-C-CH ^ -C-NH

Z \

к 1 * Я & ^

MKNjCN

MKH CIjCNjC N

_? j

MKN CN

-f-4-l • r-4-CI « _} · -4 Г CNj-4 ·· Э-І-4-СІ

-CN -4 -f-4-ir

Table 3 Representative malonic acid derivative compounds

10

Y '

10

R \

Cl Cl Br Br ClΓ ¹

си. г

H H N

Cl

.4CI, Mir,

.4-Cl, .4Br ₂ 1-4 »г 1-4 Cl Cl-S-Br« .g, Cl- * Br СІ-4 Br CH 4 Br 4.g _г

ВСД 0СД 0СД 0СД

ОН

осд ос_

- сд

^5Сй г ^С0 _? ^£ _г ^м »

ON.C (CH ₁ ),

L. О U.

К) ID

i-l О

CO

Qi

'V -'. 14, U

Μ «<4 · W '- ι»'

* ι ι ι Iff U *

Пи · · Λ ι - W

• Ж · ι · V t ι

п ы Ж X ш S

«A

W X

* jf J -, β ι 1

5 «'І' ж ¹ · ~» 'Hu "i Δ A І

β) *>

Οί

0 £

η іч

ж η . ж ^ Я " <~ <» * " ^W Pt

* X β IN · Ж T <N Z Ж fw Z С Ж

«To W

⁵ " ^S , SS" ^m

(D <0

cg

⁸ ~

sen * "!" "^

S a α a if

Ui if

X Г XX

•1

4 з "rf * rf ·

Table 4

Representative malonic acid derivatives

11

Y ¹

Y '

M й и и H 0 " г сд-4 с. г сд-4 сі г сд 4 ir и H и и и OCH гсд-4-tr 4 Cl H и и H и он 4 tr N и и H и осд 1.1-Cl ₁ N и N H ^си з он г сі 4 tr И H и H CH ₁ ONi г ι 4 ir N H N H аи. IH Cl И и и и ^сн і OC ₂ H ₅ 3 Г 4 Ir И и и H ^сн з он г Ch ₁ 4 ir и H H H H он г CH ₁ 4 ir M H H H H OCH г »4 сі и и H и H " ^нг г сн 4 ei и и и H H OHH N и CH, H и он Cl Cl ^си з и и OK

• s w w "* 4; s 3 s is s: i: -5«

»Ί i i ίΐ I І h! 3 <

L.O LL

SS

col

5 SS w ZZ

to to

с © σ

 υ

CVI

чт S Z

co

L. Φ -D Φ

U 3: (0 0)

C O Γ-Ι CD

со

CO

ο:

Οι

to

s

CM

XXX

CM N

со

U.

(D i-l ι-Ι (D.

СО

T "

К) H

CM

Table б

Representative malosauric derivative compounds

Y 20 | 18

19

17

Z ¹

13

R '

и и и и и и и и и H и и M и СИ, СИ, ti CI и и си. и 3 cl Cl и H и и и и и и

и и

tu ¹

chj

^{£ и} з ^си з

H и г сн 4 иг и и г сн, 4 нг и и 4 cl и и г сі 4 ві H H г 1-4 Br и и г си -4 нг и ^сн з 3.4 Br и и 4 Br и M гтгсі СИ, СИ, 4 cl ^сн з и 3 14 cl ^сн з и г Cf, -4 Hr и и г.4 he H и 3 гг-4 Cl H H г ei о 4 ι H и г сі 4 ι

BCH ₂ CH ₂ SO ₂ CH, OCH ₂ COCH, OCH (CH ₁ ) CjM OICI CH SO СИ ОН

О N ..СИСИ,

SCH,

SCH ₂ CO ₂ CH,

ОСИ CH ОН

ОСИ CH ОСИ СИ ОН

оси си он

OCH ₂ COCH,

(D

• Η -Q

L. ©

ι_

"j

(D (О

: СО

ία φ о:

ro

аnd

CM

14 iV »» »CN»

Чч т *

k u

CM CM

ro

CM> - > \ / ^> Cl) = O

CM 'N / OaO

in front of "H CM CM -

q;

CM

to

CM

χχ ΰ

CM CM

CM

Table В

Presenting malonic acid clarificatvurbinc junqei i

CCT

^ ѵ - ^ - і; - * ¹ 27

и и

15

Y '.

14

Z ¹ 1b

CII. CH..CH..CH LlL ₁

-CH CH ₂ Cl -CH ₂ CH-

и и

S Ü

и и и

NH ₂

SCH ₂ CH ₂ UH SCH,

2,4тС1 ₂ 2-ВГ-4-СИ

6

4 Cl 3,4-гг 3-Ur-b-Cl

2-С1 ₃ -4-Вг

O U.

IDl-l r- * (D -Q

W 3 W U

CNJ

QO CM

Table 9 Representative malonic acid derivative compounds

16

γ ·

31

R ·

15

и H H и H и и и сн _э CH ₃  г и.с- N HC- ^С Л CH ₁ O- Си, и и CH ₁ O HC- CH ₁ O г V CHO-

S S

S S о о

ICO 2.4 Cl ₂ 2.4 Of ₂ он 4С "| ^И оси г-сі-4-or «Дсод 2.4 Cl имен г (4 сі HH ₂ 2.4.S-Cl ₃ осд гісі-4 or 2.4 Cl ₂ SC И 4 Or мисносд г ог-4 сн

Table 10

Representative malonic acid derivative compounds

γι γι

34 / ^Y 33

'' VT *

32

ζ ·

и и ИИ OC ₂ H ₄ он э H г см 4 ііі и и ИИ OC ₂ H ₄ oc ₂ H _s г 1-4 »г и и NH осд vs г г 4 сі и H NH vs 3.S Cl ₂ и и NH он 3.4 ir и H NH оси 2.4.S-CI ₍ ^си з ^си з и NH ^ос г ^н $ г сн _з 4 i'f си, H ИН OCH ₁ 3.S вг З 3 ^{£ М} H ш "Cl ^си з H N (CH ₃₎ OCH ₂ CH ₂ O 3 1 4 «r ^сн з CH H О г 3.4 Cl 3 СИ, H и S NH 2.4 Cl ₂ г сн _з 4 к sri 1 СИ и ИН г сн ₃ о 4. ·. et CH. ИН 4 cl

~~ Α Z

X MX

L. О LL

а:

см го

ІІІІІІо "

иІІІ

555555255

2 5 5 5 5 5 5 5

к "

К)

* ζ j. j, +

L. О LL

CK

г ί

CM

5 5

"• aw

to red

table Representative malonic acid derivative compounds

γι γι

^γ 37 ; зб

γ ·

Y "

35

18

R '

17

Ν "

NH

JO

Cl

ОС

О) • мΙΟ LL

(Dl

in

vo -ro ^

to /

ω a:

Qi

о; in

fO

> o-o

w / o = o> - ω

о:

co и

to.

to

>

It is believed that the subject compounds set forth in Tables 1 to 11 above are examples of malonic acid derivative compounds that can be used to retard plant growth in accordance with the present invention. However, the invention is not limited to the use of these compounds alone, but includes the invention also the use of the malonic acid derivative compounds of the formula 1 mentioned above. The novel malonic acid derivative compounds according to the invention can be represented by the following formulas:

R ^ Y ^ i-CH ^ -Y ^ y "^^ ¹ ^ (i)

in which represent:

Z ₁ is independently substituted or unsubstituted halo, haloalkyl, polyhaloalkyl, polyhaloalkoxy, alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfinyl, aryl, aryloxy, arylthio, arylsulfonyl, nitro, cyano, dialkoxyphosphinyl, acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino, sulfonylamino , Alkylsulfonylamino, acyloxy, alkenyl or -CH = CHCH = CH-;

η is a value between 0 and 5;

Y ₁₁ is O, S or NR ₇ , wherein R _{7 is} hydrogen or alkyl; Y ₁₂ is O, S, NH or N (alkyl); andRg is ammonium, alkylammonium, polyalkylammonium, hydroxyalkylammonium, poly (hydroxyalkyl) ammonium, an alkali or alkaline earth metal, or substituted or unsubstituted hydroxyalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkylaminoalkyl, dialkylaminoalkyl, aryl, mercaptoalkyl, alkylthioalkyl, arylthioalkyl, aryloxyalkyl, alkylsulfonylalkyl, alkylsulfinylalkyl, acylalkyl , Aroylalkyl, dialkoxyphosphinyl

alkyl, diaryloxyphosphinylalkyl, hydroxyalkylthioalkyl, hydroxyalkylsulfonylalkyl, alkoxyalkylthioalkyl, alkoxyalkylsulfonylalkyl, poly (oxyalkylene) alkyl, cyanoalkyl, nitroalkyl, alkylidenoaroino, carbamoylalkyl, alkylcarbamoylalkyl, dialkylcarbarooylalkyl. Aminoalkyl, acylaminoalkyl, acyloxyalkyl, alkoxycarbonylaminoalkyl, cyanoaminoalkyl, carbaraoyloxyalkyl, alkylcarbamoyloxyalkyl, dialkylcarbamoyloxyalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonylthioalkyl, aminosulfonylalkyl, alkylaminosulfonylalkyl or dialkylaminosulfonyl;

T Ж ^ T

in which represent:

Z ₂ is an independently substituted or unsubstituted one Halogen, haloalkyl, polyhaloalkyl, polyhaloalkoxy, Alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfinyl, aryl, Aryloxy, arylthio, arylsulfonyl, nitro, cyano, oialkoxyphosphinyl, Acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino, Sulfonylamino, alkylsulfonylamino, acyloxy, alkenyl or

-CH-CHCH-CH-;

η is a value between 0 and 5;

Y ₁₃ is O, S or NR _g , wherein R _{g is} hydrogen or alkyl; Y ₁₄ is O, S, NH or N (alkyl); Y ₁₅ and Y ₁₆ are independently hydrogen, alkyl, halogen, alkoxy, Alkylthio, alkenyl, alkynyl, hydroxy, cyano, nitro, formyl, Amino, alkylcarbonyl, dialkoxyalkyl, alkylcarbonylamino, formyl

araino. Hydroxyalkyl, haloalkyl or polyhaloalkyl, provided that when Y _{15 is} alkyl, then Z _{2 is} not halo or polyhaloalkyl in the para position and that at least one of Y ₁ C and Y ₁₆ is other than hydrogen;

Y _- - and Y ₁₁₁ - can be linked together to form a substi

15 Ib

substituted or unsubstituted heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridging ring system which may be saturated or unsaturated; and R _Q is hydrogen or R ₅ ;

in which represent:

Z is independently substituted or unsubstituted halo, haloalkyl, polyhaloalkyl, polyhaloalkoxy, alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfinyl, aryl, aryloxy, arylthio, arylsulfonyl, nitro, cyano, dialkoxyphosphinyl, acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino, sulfonylamino , Alkylsulfonylamino, acyloxy, alkenyl or -CH = CHCHeCH-;

η is a value between 0 and 5;

Y ₁₇ is O, S or NR ₁₁ , wherein R ^. Is hydrogen or alkyl; Y ₁₈ is 0 or S;

Y _lg and Y ₂₀ are independently hydrogen, alkyl, alkoxy, alkylthio, halo, haloalkyl or polyhaloalkyl; or Y ₁ Q and Y ₂ Q may be linked together to form a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic

Ring system and a bridge ring system, which may be saturated or unsaturated; and R ₁₀ is hydrogen or R _β ; and

(Iv)

in which represent:

R ₁ and R ₂ are independently a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridging ring system which may be saturated or unsaturated can; or R ₁ and R ₂ are independently hydrogen or derivative salts, or a substituted heteroatom or substituted carbon atom, or a branched or straight chain containing substituted or unsubstituted, two or more carbon atoms or heteroatoms in any combination; Y ₁ and Yp are independently a substituted or unsubstituted heteroatom;

Y, and Y. are linked together to form a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system that is saturated or unauthorized

can be saturated; and

Y ₅ and Υ- are independently oxygen or sulfur; in which the permissible substituents for the abovementioned forms (i) to (iv) are Z with the meaning explained above

The novel malonic acid derivative compounds within the scope of formula (iv) can be represented by the following formulas:

in which represent:

Z. is independently substituted or unsubstituted halo, haloalkyl, polyhaloalkyl, polyhaloalkoxy, alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfinyl. Aryl, aryloxy, arylthio, arylsulfonyl, nitro, cyano, dialkoxyphosphinyl, acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino, sulfonylamino, alkylsulfonylamino, acyloxy, alkenyl or -CH = CHCHaCH-;

η is a value between 0 and 5;

Y ₂₁ is O, S or NR ₁₃ , wherein R _{13 is} hydrogen or alkyl; Y ₂₂ is O, S, NH or N (alkyl);

Y ₂₃ , Y ₂₄ , Y ₂₅ and Y ₂₆ are independently hydrogen, alkyl or halogen; and

^R 12 ^{is hydrogen} or R ₆ ; or

Il

^Κ 14 " ^Υ 28" ° "

^Υ 33 ₄ /

γ У \

34 ^

/ ^Υ 31

in which represent:

Ζ_ is independently substituted or unsubstituted halo, haloalkyl, polyhaloalkyl, polyhaloalkoxy, alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfinyl. Aryl, aryloxy, arylthio, arylsulfonyl, nitro, cyano, dialkoxyphosphinyl, acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino, sulfonylamino, alkylsulfonylaraino, acyloxy, alkenyl or -CH = CHCH = CH-;

η is a value between 0 and 5; Y ₂₇ is O, S or NR ₁₅ * wherein R _{15 is} hydrogen or alkyl;

28

is 0, S, NH or N (alkyl);

^Y 29 ' ^Υ 3Ο * ^Υ 31 * ^Υ 32' ^Υ 33 ^{and Υ} 34 ^{are independently} hydrogen,

Alkyl or halogen; and R _- . is hydrogen or R, -;

(Vii)

in which represent:

Z _g is independently substituted or unsubstituted halo, haloalkyl, polyhaloalkyl, polyhaloalkoxy, alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfinyl. Aryl, aryloxy, arylthio, arylsulfonyl, nitro, cyano, dialkoxyphosphinyl, acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino, sulfonylamino, alkylsulfonylamino, acyloxy, alkenyl or -CH = CHCH = CH-;

η is a value between 0 and 5;

Y, - is O, S or NR ₁₇ , wherein R _{17 is} hydrogen or alkyl; Y_- is 0 or S; and R ₁ - is hydrogen or R-;

wherein the permissible substituents Z mentioned for the formulas (v) to (vii) are of the meaning explained for the formulas (i) to (iv)

The malonic acid derivative compounds encompassed by formula 1 and the intermediates used in their preparation can be prepared by conventional methods known in the art, many of which will be available from several suppliers. The novel malonic acid derivative compounds according to the abovementioned formulas (i) to (vii) which can be used for the process according to the invention can be prepared by reacting suitable starting materials in accordance with the conventional procedures described below, as illustrated below.

The novel Malonsäurederivatverbindungen of formula (i) can be prepared according to the following general reaction scheme:

R ₆ -Y ₁₂ -C-CH ₂ -C -Cl

Acid acceptor>

-HCl

Scheme I

wherein Z ₁ , η, Υ -, * "Y- ₂ and R- have the meanings described above" reactions of this general type for the preparation of

Malonic acid derivative compounds of formula (i) including the process conditions are described, for example, by Richter, GH, Textbook of Organic Chemistry, Third Edition, Wohney Wiley and Sons, New York, p. 486. Baumann method uses cold aqueous sodium hydroxide as the acid acceptor.

The novel malonic acid derivative compounds of formula (ii) can be prepared by the fairing general reaction scheme:

YY ¹⁶ N / ¹⁵

Acid acceptor -HCl

8 14 "" 13 О О

(Z ₉ )

wherein Z,

Scheme II ⁿ * ^Y 13 ' ^Y 14' ^Y 15 * ^Y 16 ^{and R} 8 explained ^{the ODs}

Meanings of reactions of this general type for the preparation of malonic acid derivative compounds of formula (ii) including the process conditions are described, for example, by Richter, G * H ·, s. above, according to the known Schotten Baumann method described

The novel Malonsäurederivatverbindungen of formula (iii) can be prepared according to the following general reaction scheme:

10

20

^Y 18 - S - ^C

с о

' ^C1

Acid acceptor -HCl

10

γ γ

V ¹⁹

'а - с - с - с - Y ₁₇ -

З'п

Scheme III

where Z ,, n,

i8 ^{f Y} l9 '

^Y 20 ^unc * ^R l0

^ODen explained

Have meanings. Reactions of this general type for the preparation of the malonic acid derivative compounds of formula (iii) including the process conditions are described by Richter, G.H., supra, according to the known Schotten-Baumann method.

The novel Malonsäurederivatverbindungen of formula (iv) can be prepared according to the following general reaction scheme:

^R l ' ^Y l - if -

Acid acceptor

- ^Cl

* ^R

Y Y

³ \ / ⁴

C-C-C i! и

^Y 5 Y

-Y ₀ -R 2

Scheme IV

wherein R _-

Y _e and

the above explained

1 '2' 1 '2 * 3' 4 * 5 meanings. Reactions of this general type for the preparation of malonic acid derivative compounds of formula (iv) including the process conditions are described, for example, by Richter, GH s. above, according to the well-known Schotten Baumann- drive before described.

The novel Malonsäurederivatverbindungen of formula (v) can be prepared according to the following general reaction scheme:

25

'26

22 and 0

24

- C - Cl O

Acid acceptor -HCl

^R 12 " ^Y 22

C-C-C-Y-

Scheme V

where Z ,, n, Y "

and

the above

"4 ·"'' 21 '' 22 '' 23 ' ^Τ 24' ^Γ 25 ' ^Γ have meanings reactions of this general

Type for the preparation of Malonsäurederivatverbindungen according to Formula (v) including the process conditions become the Example of Richter, G.H., s. above, according to the well-known

Schotten-Baumann method.

The novel malonic acid derivative compounds of the formula (vi)

can be determined by the following general reaction scheme

produce:

^R 14- • ^Y 28- 0 It C - ^Y 33 ₄ Y C ^ ³² ^ c ^{/ YS1} C II - PI / 30 \ O ^> II - Cl LJ • Π 4 Acid acceptor R ₁₄ - ^Y 28 Y33 / ^C \ / 30 O Il -HCl 0 Il - C ⁴ C C / ^4Υ 29 ^Y 27 n, Y ₂₇ where Z is ₅ , scheme VI • ^Y 33 ' ^Y 34 • ^Y 28 ' ^Y 29 ' ^Y 3O'. 51 * ^Y 32

and R ₁₄ the

Reactions of this general type for the preparation of malonic acid derivative compounds of formula (vi) including the process conditions are described, for example, by Richter, 6.H ,, s. above, according to the known Schotten-Baumann method.

The novel Malonsäurederivatverbindungen of formula (vii) can be prepared according to the following general reaction scheme:

^Y 36 O II • II Γ _ - γ L J O Il r » - Cl • ^hy 35- (: ^Y 36 O Il - Y fi ~ * Acid acceptor 0 Il / » ^Y 35 \ -HCl ^R 16

56 Scheme VII

in which Ζ, η, Y _35, ^Y 35 and R _{16 have} the meanings described above. Reactions of this general type for the preparation of malonic acid derivative compounds of formula (vii), including the process conditions, are described, for example, by Richter, GH, s. above, described in accordance with the known Schotten-Baumann method.

In addition to the above-mentioned process, for example, other processes which can be used for the preparation of malonic acid derivative compounds according to formula _1 and the intermediates required therefor are described in the following references: Breslow, DS · et al., 3our. Araer · Chem. Soc. 6 (5, 1286-1288 (1944); Svendsen, A _# and BoIl, PM, Oour. Org. Chem. 40, 1927-1932 (1975); Sen, AK and Sengupta, P., 3. Ind. Chem. Soc. 46, (9), 857-859 (1969); Thiers, R. and Van Oormael, A., Bull. Soc. Chim. Belg. 61, 245-252 (1952); Brown , RFC, Australian Journal of Chem., 8, 121-124 (1955); U.S. Patent 3,951,996; British Patent 1,374,900; Chlriac, CI ,, Revue Romaine de Chimie 25, (3), 403-405 (1980). Weiner, N., Org. Syn. Coll., Vol. II, 279-282 (1950), Sixth Printing, Oohn Wiley & Sons, New York; Block, Or., Paul, Org. Syn. Coll. Vol. V, 381-383 (1973), CJoKn Wiley and Sons, New York; Reliquet, F, et al., Phos. And Sulfur 24, 279-289 (1985); Palmer, CS., And McWherter, PW., Org. Syn. Coll., Vol. I, 245-246 (1951), 2nd Ed., Oohn Wiley and Sons, New York; Straudinger, H. and Becker, H., Reports 50, 1016-1024 (1977); Purrington, ST and 3ones, WA, 3. Org. Chem. 48, 761-762 (1983); Kitazurae, T. et al., Chem. Letters (1984) 1811-1814; Wolff, IA, et al., Synthesis (1984 ), 732-734, Zambito, Α · 3 · and Howe, EE, Org. Syn. Coll. Vol. V, 373-375 (1973), 3 Wiley and Sons, New York; and Curing, WH et al., Org. Syn. Coll. Vol. V, 376-378, CJohn Wiley and Sons, New York.

Further illustrative methods that can be used to prepare malonic acid derivative compounds of Formula I ₁ and the intermediates necessary therefor are

for example, in the following references: Rathke, MW and Cowan, PO, 3rd Org. Chera. 50, 2622-2624 (1985); Hairdryer, WS. Org. Syn. Coll. Vol. IV, 293 (1963), Oohn Wiley and Sons, New York; Gompper, R. and Topfl, W., Chem. Bor. 9, 2861-2870 (1962); Gompper, R. and Kunz, R., Chem. Ber. 99, 2900-2904 (1966); Ono, N. et al., 3rd Org., Ex. 50, 2807-2809 (1985); U.S. Patent 4,154,952; Blankenship, C. and Paquette, LA, Synth. Comm. 14, (11). 983-987 (1984); Baldwin, OE et al., Tot. Lett. 26, (4), 481-484 (1985); Kawabata, N. et al., Bull. Chem. Soc. Ορη. 55ί, (8), 2687-2688 (1982); Bodanszky, M. and du Vignaud, V., 3. Am. Chem · Soc. 81 . 5688-5691 (1959); Neelakantan, S. et al., Tetrahedron 21, 3531-3536 (1965); U.S. Patent 4,020,099; 3A-PA 148,726 (1979); Fuson, RC, Advanced Organic Chemistry, p. 202 (1950), 3 by Wiley and Sons, New York; Duty. R. C., Anal. Chem. 49, (6), 743-746 (1977); Korner, G., Contradi, AHi acad. Lincei 22, T, 823-836 (CA 8, 73 (1914)); Schimelpfig, CW, 3. Chem. Soc. Perk, Trans. I, 1977 (10), 1129-1131; Kim, YS et al., Taehan Hwahak Hoechi 18, (4), 278-288 (1974); DE patent 2,449,285; U.S. Patent 3,962,336; and US Pat. No. 3,992,189.

Co-pending US Patent Application Serial No. (D-15299), filed on even date, discloses the use of malonic acid derivative compounds of formula _1 for crop yield enhancement. Co-pending US Patent Application Serial No. (D-15298), filed on even date, describes synergistic plant growth regulator compositions comprising (i) an ethylene reaction or an ethylene-type reaction inducing agent and (ii) a malonic acid derivative compound of formula I ^ included. These two applications are incorporated herein by reference.

It has been found that the malonic acid derivative compounds according to formula 1 significantly retard the plant growth in comparison with untreated plants under the same conditions. Moreover, the malonic acid derivative compounds of the present invention are not substantially phytotoxic to growing plants.

As used herein, an effective amount of a malonic acid derivative compound for retarding plant growth refers to an amount of compound effective to retard growth which is sufficient to retard plant growth. The effective amount of the compound may be over a wide range depending on the particular compound used, the particular plant to be treated, the environmental and biological conditions, and the like.

The preferably used amount of the compound does not cause substantial phytotoxicity to the plants such as leaf burns, chlorosis or hcrose. In general, the compound may preferably be applied to the plants at a concentration of about 0.01 to 15 pounds of the compound per acre (0.0112 to 16.30 k ~ / ha), as described in detail below.

The malonic acid derivative compounds encompassed by Formula 1 can be administered by a variety of conventional methods known to those skilled in the art. The compositions containing the compounds as active ingredient typically comprise a carrier and / or diluent in either liquid or solid form.

Suitable liquid diluents or carriers are water, petroleum distillates or other liquid carriers with or without surfactants. Liquid concentrates can be prepared by dissolving one of the compounds with a non-cytotoxic solvent such as acetone, alkylene, ITitrobensen, cyclohexanone or dimethylformamide and dispersing the active ingredients in water with the aid of suitable emulsifying and dispersing surfactants. The number of dispersing and emulsifying agents and their amount used will depend on the nature of the composition and the ability of that agent to facilitate dispersion of the active ingredient. In general, it is desirable to dec in accordance with the desired dispersion

active ingredient in the spray, to use as little of the lotion as possible, so that the active ingredient, after being applied to the plant, can not be re-emulsified by rain and washed off the plant. Hichtionogenic, anionic or cationic dispersing and emulsifying agents can be used, such as the condensation products of alkylene oxides with phenolic and organic acids, alkylaryl sulfonates, ether alcohol complexes, quaternary ammonium compounds and the like.

In the preparation of surface active powders or dust compound compositions, the active ingredient is dispersed in and on a properly divided solid carrier such as clay, talc, bentonite, diatomaceous earth, puller earth and the like. In the formulation of the surface-active powders, both the aforementioned dispersants and lignosulfonates may be included.

The required amount of the active ingredient of the invention may be between 1 and 200 gallons (3.785 and 757 liters) or more of a liquid carrier and / or diluent or between 5 and 500 pounds (2.268 and 226.8 kg) of an inert solid carrier per acre to be treated and / or diluent are applied.

The concentration in the liquid concentrate is usually between 5 and 95 Maize / S and in the solid formulations between 0.5 and 90 liquid / 5. Generally, satisfactory sprays or dusts for general use contain between 0.001 and about 100 pounds of the active ingredient per acre (0.001 and 112 kg / ha), preferably between 0.01 and about 15 ^ pounds of the v / i wk constituents

-59a-

per acre (0.01 and 16.8 kg / ha) and most preferably between 0.1 and about 5 pounds of the active ingredient per acre (0.112 and 5.60 kg / ha).

The formulations useful for the practice of the invention may also include other optional ingredients such as

For example, they contain stabilizers or other biologically active compounds which do not affect the efficacy of the active ingredient and damage the plant to be treated. Other biologically active compounds are, for example, one or more insecticidal, herbicidal, fungicidal, nematocidal, miticidal, plant growth regulators or other known Compounds "Such combinations may be used for the known or other purpose of each ingredient and may exert a synergistic effect.

The malonic acid derivative compounds of Formula 1 are preferably applied to plants under substantially average or normal growth conditions. The malonic acid derivative compounds of the present invention may be applied during the vegetative plant growth phase or the reproductive plant growth phase in order to delay plant growth.

Such compounds are useful in agriculture, horticulture and related fields and can generally be applied to both nudist and hawker, in particular to vegetation such as woody plants and grasses for retarding plant growth. The compounds are used, for example, to control vegetation height in public Because of and for the growth retardation after pruning of trees and shrubs and the like without adverse ecological effects useful «

Plants in the present invention are all plants grown in agriculture and horticulture, woody plants, ornamental plants and grasses. Examples of woody plants which can be treated with the malonic acid derivative compounds according to formula .1 by the process according to the invention are, for example, maple, sycamore, red oak , American Elm, Lime, Ginko, Oak, Ash, Maple, Apple trees, Chinese Elm, Crabbeam, Russian Olive, Silver Maple,

-61-

Examples of other plants which can be treated with the compounds according to formula I _- by processes according to the invention are corn, cotton, sweet potatoes, yams, alfalfa, sugar beet, vasexes, poplars, conifers and the like , Wheat, rye, rice, barley, oats, millet, dried beans, soybeans, sugar beets, sunflowers, tobacco, tomatoes, ganola, sloping fruits, lemon fruits, toe, coffee, olives, pineapple, cocoa, bananas, sugarcane, oil palm, herbaceous outdoor plants , woody shrubs, grasses, ornamental plants, evergreen plants, trees, flowers and the like

The Llalonsäurederivatverbindungen invention are effective in the delay of plant growth. Such compounds have great safety margin in that they do not burn or injure the plant when used in an amount sufficient to retard plant growth, and they are weather resistant, including resistance to rain washout, ultraviolet light degradation, oxidation or hydrolysis in the presence of moisture or at least resistant to such decomposition, oxidation and hydrolysis which would significantly reduce the desirable plant growth retardation properties of the active ingredient or would undesirably produce properties such as phytotoxicity. Mixtures of the active compounds, as well as combinations of the active compounds with other biologically active compounds or ingredients, may be applied, as indicated above.

Execution ispi el

The invention is illustrated by the following examples.

Example I Preparation of ethyl 3 - / (4-fluorophenol) amino / 3-oxopropanoate

In a nitrogen-purged, air-stirred reaction flask, 4.44 g (0.04 mol) of 4-fluoroaniline, 4.05 g (0.04 mol) of triethylamine and 200 ml of tetrahydrofuran solvent were added. Then, a quantity of 6, 02 g (0.04 mol) of ethyl malonyl chloride added through a dropping funnel into the mixture, which was stirred well at room temperature and then was rinsed with a few milliliters of tetrahydrofuran · the temperature of stirred mixture rose to 42 ⁰ C and sat a white precipitate of The mixture was then stirred at ambient temperature for about 2 hours, the triethy1-amine hydrochloride was filtered off, washed with solvent and dried to give 5.2 g (0.04 mol). The solvent was removed from the filtrate on a rotary evaporator and the remaining purple dye was dissolved in methylene chloride. This solution was washed successively with 2N HCl (3 75 ml) and water (2 × 75 ml) and then dried over magnesium sulfate, the solvent was removed in vacuo and a solid crude product was obtained. Recrystallization from ethyl acetate-cyclohexane followed by flash column chromatography afforded 3.47 g (0.015 mol ) Ethyl 3 - / (4-fluorophenyl) amino / 3-oxopropanoate with a melting point of 68 ⁰ C to 71 ⁰ C. The elemental analysis of the product gave the following:

Analysis: ^C n ^H i2 ^FN0 3 Calculated: C 58.66; H 5.37; N 6,22 Found: C, 58.61; H 5.35; N 6,36 The compound is referred to below as compound 1 ·

63 Example II

The further compounds were prepared in the same way as in Example I. The structures and analysis values for the compounds 2 to 76 are listed in the following Table A.

Table A Representative malonic acid derivative compounds

R ^ OC-CH ₂ -C

Connection no.

^R i

Subetituenten Elemental analysis

Calculated

"Found

JL

-fcL

Iz point on

Il 12

ia

14 It 1 »

сд сд

^С 2 ^И *

сд

^С 2 ^И »СД

^С 2 ^Н | СД

-Cl - CN -СД

- "j-4-ir

-f-4-Cl-S-r (.O) (OCH CM)

i-CHj-4-Or

-Cl

-СІ-4-Г 2-CI

N (CHj) S "-3" S.S2 P. 40 S4.2S S.S3 І.21 4t-S2 NH "2.0" p.21 1.12 "L." 0 S.Ot 1І.И 101-103 NM "3.0" ".SI 43. H ".SI »I · 10 HN 41.OS 4:02 41.0 » 4.14 41-41 NH 40.10 Э.ІЭ 40th d 3.24 »T-12 NH 4S.S2 S.И 4S.4I P. 2 » HM m 4t. "T p.13 I 41.43 p.41 I I41-14S ни 40.01 4.10 4t.2S P. 24 I M-4S "и S2.M 4.3 » Sl.tt 4.S3 11-12.S NH S4. "L Sol S3. " p.33 • ti • 41.U 1.И 44.43 1.0 » • ti NH M.M 1.20 "t.S2 1:00 00-M NH »» .3 " 1.20 ".2t 4 1.2 ' U-IO NH SO.H 4.21 S0.S2 4.10 U-Il NH Я. »J S.OI S4.S0 S.Il S4-S1 1:32 p.34 S.OI S.OO l.t " I.ti I.S4 I. S * 1.4 » I.H l. "1 I. "S I.Ot p.22 in the 1.0 * - - LIS in the > ts ".to .3t I.It .00 I.12

Table A (cont.) Representative malonic acid derivative compounds

0 0 ti Η RJO-C-CH ₂ -C -Y ^ -

Compound pr No. 1

Substituents ^ Elementaranalyee

Calculated

Melting point

hours

II

IO C ₂ N, M го 21 22 23 СД! 24 CN J 2S 2t г.і- (сн ₃ ) ₂ 21 1-СГ ₃ -4-ГЛ ! .S-Cl .S-Or ₂ -CH ₃ -S-Cl .4.S-CI, СД 2-CH ₃ -4- £ l СД 2.4Cl ₂ СД 4-CH ₃ S-

NNR (COCl ₃ ): /1.11-1.39 (t.3N). 2.33 (ЭН). 3.45 (p.2H). 4.01-4.42 (Ч.2Н). IM-I.Я («.4И). 8.9-9.3 (see also И) ри.

NW (COCI ₃ ): / 1.1S-1.41 (t.3H). 2.23 (s.tH)

 2.50 (s.2M). 4.01-4.SO (Ч.2И). 1.10 (p.3N)

0.31-0.18 (br sN) цт.

00-03

<1-Ι00

IN THE 4 *** 4 3-sa 4лг 4t. "0 3.11 4:41 SO.S-H NH 4I.0S 4:02 S.OI 41.04 4.0S S.OI 12-1S NN 4I.0S 4:02 S.OI 41.11 3. · " 4. " M-M NH 3t. 1" 3:04 3:04 st.st 3.11 Э.11 NH St.37 S.S2 P. 48 St.lt P. 12 S.2t M "8 NH 42. S4 3.2s 4.Sl 42.9S 3.1T 4.20 111-113 NH St.31 S.S2 P. 48 St. 00 S.ti p.21 103-104 НИ 4I.0S 4:02 S.OI 41.J1 4.0S 4.1 * UU NH St. " P. 91 S.S3 St. Is S. IO P. 48 13-IS

Table A (Forte) Representative malonic acid derivative compounds

R JO-C-CH ₂ -C- Y 1 -VJ?

Connection no. LLI LTI substituents j t-CH.O-S-Cl Y ' calculation Elementaranalyee efuncfen (^ η 3.21 JL 4.02 Melting point U / -> 20 ung ρ · z \ J Il НИ 4S.4t: net 4S.tt p.11 p.14 C 12-IS 2t CH ι I-C HO- ИИ Jl.04 ί 1.21 < Sl. tS l.M 4:00 Ot-Ol M Z »CH C 9! - • -С И - ИИ м.м: Lit It.M 1:01 S.I1 100-110 11 Z * C.H I 4 t ИИ t2.11 t l.tl * ti. " t.2t S.M 100-101 32 2 S с, и ι l -.- C И0- ИИ M.41 I 1.02 ' M.ti I.IS 4.S0 Oil 11 Z i ι 4 t ИИ M.42 I 1.04 · ti.It I.IS 4.11 M-M _M Z S CH Г.4-0Г * ИИ 14.4t 1.20 ι ts.ot l.M 4.1t 02-03 IS ZS ^C A i Г-СІ-4-Ог ИИ 42.44: I.SO! 42.40 TTtJ 37Π 104-1OS 34 2 S C, H • t-Of-4-Cl шг It.11 1 I.2S < Л .71 1:42 4.3S II 2 % Ot i I-C ^ HjCO- ИИ 41.21 3 I .Of 3 4i.г " 3.tl 4.SS It-M M 2 S СИ 1.4 іг _г ИИ 41.21: l.4t 4 41.St S.Sl 4:40 01-01 M Z 3 C-H. t-r-4-Or ИИ t.44! l.4t 4 tt.IS 1.11 3rd st Ot-Ot.S 40 Z 9 с, и t-CH ^ O-4-CI ИИ u.it : ι.Sl 4 It. 21 l.M ! .ti M ti 41 Z S CH ИИ 41.44 i 1.04: 41.4t P. 21 S.IO It.s-M 42 Z 9 си ИИ S1.04 1 .ti 4 Sl. 30 H-Il Z 9 сд .It 9 1:00 > .lt 1.20 t.SI t.32 I.St (.01 LSI 1:04 LLI .11 I.SO 1:04 .ti .it

Table A (cont.) Representative malonic acid derivative compounds

connection 43 ^R i substituents ^Y i Elementaranalyee Calculated C _H N Found C H N enamel No. 44 C ₂ H ₄ NH 41.00 4.20 4:50 41.31 4. "4 4:59 Point 45 NH 4 ·. "! 4:52 4:03 49.0 ' I. "2 4:49 MC 4 ' ^C 2 ^H S 2-CM ₃ O-4.S-Cl ₂ NH 50.00 4.21 5.3 · 50.90 05.01 " 5.21 95-90 41 C ₂ H ₄ 2-СИ -3.4-CI NH 41.21 3.4 ' 4.31 41.2 ' >. "! 4.14 90-93 40 • СИ 2-Г-4-С1 NH 51.23 5:53 4.21 SIS " І.4І 4.11 "" - "9 C ₂ H ₄ 3-Or-S-Ct NH NNO (OH SO * _t ): J 1 . «- 1.43 (t. 3:40 10-00 4 * 2-CM -4-Or (P.2H) , 4.04-4.1 (· 4HJ 1.5-0.1 (·. ЗИ) »·. 91-M 50 C ₂ N ₄ 2-CO ₂ MI-Ir NH 4t. "1 4. $ 2 - 4 «.22 < 1:43 - 151-154 51 C ₂ H ₄ NH 4 ·. "! 4:52 4:03 49. «0 ' 1:40 4.4S 52 C ₂ H ₄ 2-CHj-SS-Cl ₂ NH 51.09 5 M 5.19 50.2 «I І.04 5.24 IU-IIO 53 C ₂ H ₄ 2-CH-Cl ₂ -4.S NH 5 *. 31 5:52 5:40 S * .49 i p.49 5:41 134-135.5 54 ^C 2 ^H 5 2-СД-4-СІ NH 4 ".OO 3:01 • .11 4 «.S2 ' 1:00 9:43 N-M 55 2-CH-Э-С1 NH "S.I4 T.03 "33 43.40 I I.SI ".12 103-105 5 ' C ₂ M ₄ 3-NO 4-CI NH "0:15 ".31 SiO «0.02 ( (.20 5:04 01-03 2-CH NH 51.33 4.91 4:41 SI. "5 * 1.92 4:33 "0-11 2-CM ₃ O 42 * 4 2.S- (CM ₃ J -3.4-CI 119-120

Table A (Fort9) Representative malonic acid derivative compounds

0 0

и и

² i

Compound _p , No. "l

substituents Elemental analysis

Calculated

шиш

ends

Melting point

sl

St

СД

l-CHj-4-ir-S-CI

NM MM MM

3. «4.H

4. · 3 4.2 ·

41.10 4th »

4I. «S 4.31

ti.21 4.t4

4.41 ·· - · *

Э.І2 IJI-IJi

4.14 M-ai

OCH _x -

"Mj

Sa.SS S.It 3.41 S ·. ·! P.23 3.2 * OtI

СД

4

MM

11.31 ».st 3.« 10.91 *. «3.12« 100

Table A (Forts,) Representative malonic acid derivative compounds

II

substituents Elemental analysis

melting

Connection number * cV Z ^ 4 -Or ^Y i Bnrechnet p.13 4th st _? efunden ti kl Point ΙΜΓ · (2 C, H з-с.н.о- MH "0:22 3.12 4.1 ' "O.IS H- 4. «« O Oti C 1 с _э н _с «P 2-CO ¹ CH 4-Or HH 4 ".13 s.oo p.44 4 ". OS 4.12 Oil "4 2 p 2.1 (СИ.СИСИ.Сй) 2-0Г-4 CHj MH 2.10 ".32 ".1" 10:30 S.SI M-M "S с, и. M * -Ci " MH "3.1" 4:02 S.01 "3:44 1:03 Oil (4 2 p 3.4-CI 3. S-CI HH 41.OS 4.3 ' SO" 41.1 ' S.M 00-01 "I С И 4 Cr. 2-CH4-Or MH S2.31 4:00 11:11 S2.ll s.II H-HS M 2 p 3 20 ^ -4-0 ^ 0 MH S2.M 4.23 4. "0 S2.20 11:14 "0-101 2 2 3 CH MH 4 ". Il 4 m. - 41.11 4. "l «« -M 2 p July Д? _2Ж 4.10 4:01 ".Si - Mt " 11 • -C.H NH 4S.3I 4.10 4.tl 4S.ll 4.2 ' "•-IN THE 12 4 «С И HH 40.02 "20 10.1 ' 40.3S 4.S " "Ι- · 4 13 2 p NH . "4 "0 3:44 - "4:13 10. "4 SO-S3 14 S "SO* 4.10 4.ti 44.01 - Oil is MH 40.02 "03 S.Sl 40.10 t 4.11 114-11 " 1" HH "2:14 "1:41 I p.30 10 '-1IO JX 1.04 1:41 .M I.S4 .M .st .21 .it \ лг 1:01 1:00 к.2 " I. "β I.OS к. 10

Example III

Preparation of ethyl 1- (2-methyl-4.5-dichlorophenylaminocarbonyl) cyclopropanecarboxylate

In a nitrogen-purged round-bottomed flask was added 5.53 g (0.03 mol) of 2-methyl-4,5-dichloroaniline. Add 3.18 g (0.03 mol) of TYiethylamine and 190 ml of tetrahydrofuran solvent. With vigorous stirring, an amount of 5.55 g (0.03 mole) of ethyl 1-chlorocarbonylcyclopropanecarboxylate prepared in Example XVIII was added in one portion and the mixture was then stirred at ambient temperature for six hours. Then a precipitate of triethylamine hydrochloride was filtered off and the solvent was expelled from the filtrate under vacuum to give a light yellow solid. The solid was taken up in ether and the solution was washed with water, dried over magnesium sulfate and the solvent was evaporated; A yellow powder was obtained. Recrystallization from ethyl acetate-hexane gave 4.51 g (0.01 mol) of ethyl l- (2-raethyl-4,5-dichlorophenylaminocarbonyl) cyclopr.opancarboxylat having a melting point of 105 ° to 107 ⁰ C. Elemental analysis of the product revealed the following:

Analysis: ^c i4 ^H i5 ^C1 2 ^N0 3 Calculated: C 53.18; H 4,78; N 4,43 Found: C, 53.41; H 4.76; N 4,44

Oiese connection is referred to below as connection 77.

Example IV

In the same manner as in Example III, the further compounds were prepared. The structures and analytical data for compounds 78 to 96 are listed in Table B below.

Table В Representative malonic acid derivative compounds

substituents Eleme ntaranalve

Connection no ^R 2 4 то Vs ^! f.4.S-CLJ It vs i. <- ci ₂ to С И i (.4-Cl 2 p Oil Vs ^! ts-ci ₂ 02 Vs '' Г-Г-4-С1 03 Vs * I-CI 04 • Vs ' ι.ar OS C ₂ H, 1.4-Or ₁ M Vs ^! 1.S-Or ₂ 01 си а (.4-Or ₂ 00 C # vs ^J t-CI-4-Or η Vs ^a ! - • r-4-CI M C ₂ H, I-CM-Or ti C ₂ H, i ! -CHj-4 -Or-S-C I

Calculated

melting

4 ". 30 3.St 4 *. U 3.tt 4.10 130-132.S siti 4.34 ' Sl.tS 4:34 4.12 101-110 Sl.il 4:34 SI.21 4.S3 4:41 TS-M SI. "? 4:34 SI. 3t 4:40 4.4t 10S-100 S4.tS 4.St < S4.t2 4.11 4.0S t ".s-t * SO.32 P.21 '. SO.IS S.2t S. U tl-tj S0.02 4.S2 SO. IO 4.И 4.S2 іг-S-ts Л.К J73S: <. 0 " 3:41 ЗЛ " U0JJi_ M. "2 3.3S: 3t. 02 3:32 3.4 ' ti M.S. 3t.t2 3.3S: 40.02 3.tl 3.11 IM 103rd S 4S.04 3. »4 4S.20 3.tt Э.М IOT IIO.S 4S.04 3.10 ' 44.0t 4.2T 3:00 lit " 4S.O4 3.10 4 4S.lt 4.20 3.11 MJ-IU 44. «2 4.1t 1 40.14 4.14 3.0 ' LLT-121 t.u I. "4 IN THE I. »4 ι.to (.23 1.4t I.SO I.SO I.SO 1:04 1:04 1:04 1:00

Table B (cont.) Representative malonic acid derivative compounds

H ₀ C ² \ У ^СН 2 NH - C-C -C- Il Il О О

connection

substituents

R ₂ ZA

• t • э • 4 «S« 4

Vs сд

2-Г-4-Г И

3.S-CI ₁ 4-С Jl

> -ГМ .4. »

.03 Elemental J 4. Found -JL · 4.01 4 .02 enamel . "I Calculated 4th 44.01 4.4 · S .00 Point .10 3. *? 4th 44. S4 4.S2 4 .34 ° C ν- я- 41 .SS 4:41 10th SI.Si S.SI 10 .41 102-103 M 4:34 4th 4S.02 4.14 4 .31 OS-M sl p.44 SI.J2 44-4? 44 4. "4 .24 IM IN SI .00 M-Il .44 OS 2 ·

-73-

Example Y

Preparation of 3 - / (4-bromo-2-methylphenyl) aynino / 3-oxopropanoic acid

An amount of ethyl 3 - / (4-or-2-methylphenyl) amino / 3-oxo-propanoate prepared in Example I (compound ET 75) was dissolved in about 80 ml of ethanol and 1.2 g (0.03 mol) of sodium hydroxide granules were added to the resulting mixture. The mixture was stirred for four hours and then allowed to stand overnight. The mixture was then evaporated to dryness and water was added to give a cloudy yellow solution. This solution was extracted with methylene chloride and then acidified with 10% hydrochloric acid to form a white precipitate. The white precipitate was worked up to give 1.8 g (0.01 mol) of 3- (4-bromo-2-methylphenyl) amino / 3-oxo-propanoic acid as a white pesticide having a melting point of I63 ⁰ C to 165 ⁰ C. The elemental analysis of the product gave the following:

Analysis: C ₁₀ H ₁₀

Calculated: C 44.14; H 3.70; H 5.15 Found: C 43.90; H 3.68; IT 5,11

This connection will be referred to as connection 97 in the following. Example VI

In the same way as in Example V, the other compounds were prepared. The structures and analysis values of compounds 93 to 109 are shown in the following Table C.

Table С Representative MalonsSurederivatvarrn nn, _tn ,

о о

R 1 is OC-CH ₂ -CO-

Connection no.

substituents

Calculated

Elementaranalysa

Gefundan

melting ·

IN THE

102 103

104 105 IM 101 IM

Cl -01, -4-Ir-I-Cl

F-4-Or

г-ог-4-CMj

г-вг-4 egg г-сі-4-or

2.4-Or,

3-C 1-4-C

3.11 «.5« 50. «1 3.00 t.31 140-141

2.M. 4.51 39.3 «3.14 4.44 101-102

2.09 4.1 «32.34 2.33 4.04 U4U5.S

2.5 «5.01 39.24 2.42 4.94 Ul-Ul

2.14 4.9 «30.51 2.12 4.04 114-114.5

): / 2.21 (f.3N). 1.4 (s.TM). 154-151 «.95-0.01 (Я.4И). 9.5-9.1 (brt. М) ии ».

J * .U 2.41 4.И 11ЛІ 2.1t 4.11 159-Ul

Э4.9 »2.41 4.19 31.10 2.M 4.H Ui. 5-Ul

32.M 2.09 4.1 «32.21 2.23 4.13 151-159

32.M 2.09 4.1 «31.9« 2.22 4.M 14. 4

WNi (COCi ₁ ZImSOd ₆ ): J г.49-г «4 (ьо.н). э.5г (* .гм),

1.11-0.24 (а.З). 9.86-10.05 (br S.H) pp «.

Mm (COCI ₃ ZONSOd ₆ ): 4 2.30 (I.JH). 2.45-г. «Э (br t. И). З.Э4 (f.2N).

1.05-1.M (а ЭИ). 10.04-10.23 (br S.H) »» ·.

Example VII

Preparation of l- (2-Methyl _"t 4 ~ 5 dichlorphenylarainocarbonyl) cyclopropanecarboxylic acid

In a 250 ml round bottom flask, a solution containing 0.34 g (0.006 mole) of potassium hydroxide and 0.109 g (0.006 mole) of water in 80 ml of ethanol was prepared. Cooling to a temperature of 0 ^° C. in an ice / NaCl With stirring, a solution of ethyl 1- (2-methyl-4,5-dichlorophenylaminocarbonyl) cyclopropanecarboxylate prepared in Example III was added in a small volume of ethanol, then the mixture was heated to room temperature over a period of time The mixture was stirred in vacuo to give a white solid residue which was dissolved in water and extracted twice with ether. The ether extracts were discarded. The water solution was acidified to pH 2 with 25% HCl solution to precipitate 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 and gave a white solid. This white solid was washed with water and dried in a vacuum oven to give 1.85 g (0.006 mole) of l- (2-methyl-4,5-dichlorophenylaminocarbonyl) cyclopгораncarbonsäure having a melting point of 248 ⁰ C to 251 ⁰ C. Elemental analysis of the product gave the following:

Analysis: ^{C H} l2 ll ^C1 2 ^N0 3 Calculated: C 50.02; H 3.85; N 4,86 Found: C 50.51; H, 4.31; N 4,83

This connection is referred to below as connection 110.

Example VIII

The further compounds were prepared in the same manner as in Example VII. The structures and analysis values of the compounds H1 to 128 are listed in Table D below.

Table D Representative Malonic Acid Derivative Compounds

HO - С - С - С - NH -Г м H О О

^Z 4

substituents connection Elementaranalvas

melting

111

112 Ш 114

ns

IU

11 · 11 * 12 «121 122 123 124 125 IM 121

12 ·

^Z 4

2-СИ ₃ -4-ІГ 2.4.S-C1,

2-f-4-C1 4-C1 4- * r

2 ~ Cl-4 * r 2-4 * -4-C1 3-C1-4-tr 2 ~ СН ₃ -4- »г - $ - С1 2-Г-4-І * 4.Cf, 3. S-Cl

(dec.) - with decomposition

Calculated ü_ - 4.06 (t.H) ppa. 3.31 JL- 4.70 Found _ü Ы_ 4.06 i .74 (И.4Н). 10.M J.tO · Point Vl C _ 2.61 41.20 4:54 4 t. 20 3.14 ι C cn 41.34 3.31 p.11 43.11 3.26 < 41.71 204.5-204 42.И 3.31 p.11 4t.33 3:40 І.04 250 4t. 20 3:52 p.44 45.24 3.70 223.5-2 " 41.20 4.21 5.14 Sl.11 4:35 1M-1M SI. 27 3.SS 4.13 54.61 3.4s P. 26 202-204 SS. 12 2.S0 3.W 46.36 2.70 217-211 46.50 2.S0 JW 37.13 2.60 220-222 36.31 2.S0 Э.М 36. "1 2.1 $ i 224-226.5 36.3t 2. "S 4:40 36.61 3.10: 211-212 16.3t 2.as 4:40 3t.74 3.2 ·! 222-22S 41.47 2. (S 4:40 41.67 3.23 - 146-164Ч «« *.) 41.47 3:33 4.21 41.70 4.0 ·: 210-211 41.47 3:00 4.64 4S.47 1.66 211-214 43.33 3.6 » p.13 43.17 1:42 231-234 43.73 1.52 (i · 4H). 7.02-7 52.73 1.16 203.5-201 52.75 Ϊ.03 115-1M.S NtM (COCl ₃ ): p.11 p.22 111-202 S.St 1:06 220-222.5 I.И Ι. · 2 1:04 I.IS I.ti 1.11 1.11 335 4.30 3.10

Example IX

Preparation of ethyl 1-i4-bromo ~ 2-roethylphenvlaminocarbonvl) cyclobutanecarboxylate

Into a reaction flask purged with nitrogen were added 2.74 g (0.01 mol) of 4-bromo-2-methylaniline and 1.49 g (0.01 mol) of triethylamine dissolved in 200 ml of tetrahydrofuran. 0.01 mol) of ethyl 1-chlorocarbonylcobutanecarboxylate prepared in Example XIX, and the resulting mixture was stirred at ambient temperature for 6 hours. A precipitate of triethylamine hydrochloride was removed by filtration. The filtrate was removed in vacuo and the residue taken up in methylene chloride. This solution was washed successively with 2N HCl (2 × 75 ml) and water and then dried over magnesium sulfate. The evaporation afforded a crude product which was flash chromatographed over silica gel using 7: 3 hexane-ethyl acetate to give 3.68 g (0.01 mol) of ethyl 1- (4-bromo-2-methylphenylaminocarbonyl) cyclobutanecarboxylate as a white solid won. A small sample recrystallized from hexane had a melting point of 61 ^° C. to 64 ^° C. The elemental analysis of the product showed the following:

Analysis: ^C i5 ^H i8 ^BrN0 3 Calculated: C 52.92; H 5.33; N 4,12 Found: C 52.99; H 5.44; N 4.05 The connection is referred to below as connection 129. Example X

In the same manner as in Example IX, the further compounds were prepared. Structures and analytical data of compounds 130 to 134 are listed in Table E below.

Table E Representative malonic acid derivative compounds

CH,

H ₂ C

CH,

R'O is -C-C-C-NH 4 and

O O

substituents

Connection No. _t ^R 4 ч 130 131 vs 3.5-CI ₂ 132 133 134 <*> с ₂ н ₅ C ₂ H ₅ ⁵ 2.4-Cl ₂ 3.4-Cl ₂ 4-Cl

Elemental analysis

Calculated

53.1t 47.95 53.11

S3.ia

59. U

4.7 · 4.02 4.7t 4.71 5.73

4.43 4.00 4.43 4.43

Found

Melting point

52. «4 47.25 52.14

53.14

4.17 3.70 4.67 4.71 5.70

4.23 3.94 5.11 5.92

7 * .S-tO 47-49 011 011

IS.t-t7

(^ prepared according to the Miech anhydride method according to Example XXXIII

Example XI

Preparation of 1- (3,5 "-dichlorophenylaroinocarbonyl) cyclobutanecarboxylic acid

An amount of 2.0 g (0.006 mol) of ethyl 1- (3,5-dichlorophenylaminocarbonyl) cyclobutanecarboxylate prepared in Example X (Compound 130) was dissolved in the presence of water (0.114 g, 0.006 mol) with ethanolic potassium hydroxide (0.355 g The potassium salt of the acid was then acidified with 25% HCl solution and worked up in the same manner as described in Example VII, yielding 0.92 g (0.003 mol) of 1- (3,5-dichlorophenylaminocarbonyl). cyclobutanecarboxylic acid in the form of a beige solid having a melting point of 159 ^° C. to 160 ^° C. The elemental analysis of the product gave the following:

Analysis: ^{C H} l2 ll ^Cl 2 ^N0 3 Calculated: C 50.02; H 3.85; N 4,86 Found: C 50.20; H-3,83; N 4,84 This connection is referred to below as connection 135 Example XII

The further compounds were prepared in the same manner as in Example XI. The structures and analysis values of compounds 136 to 139 are listed in Table F below.

Table F Representative malonic acid derivative compounds

CH,

н ₂ с

HO-C-C-C

о о

- NH - / '

connection

substituent Elemental analysis

Found

melting

137 13 · 139

2.4.5-Cl ₃ 2.4-Cl ₂

4-Cl

44.U 3.12 SO. 02 З.І5 SO.02 3. · $ S *. Il 4171

4:34

44.U 3.14 4.23 146-141 SO. 22 4.30 - 12 "-132 SO. 22 4.10 - 1S1-1S3 Sb. M 4.94 IM-Ul

Example XIII

Preparation of ethyl 1 - ^ - bromo ^ -raethvlphenylaminocarbonyl cyclopentane

Ethyl 1-chlorocarbonylcyclopentanecarboxylate (3.10 g _f 0.02 mol) prepared in Example XX, 4-bromo-2-methylaniline (2.82 g, 0.02 mol) and triethylamine (1.53 g, 0.02 mol ) were reacted in tetrahydrofuran (200 ml) under the same conditions as described in Example I to give 2.40 g (0.007 mol) of ethyl 1- (4-bromo-2-methylphenylaminocarbonyl) cyclopentanecarboxylate which, upon recrystallization from hexane, became a melting point from 64 ⁰ C to 67 ⁰ C. The elemental analysis of the product gave the following:

Analysis: ^c i6 ^H 20 ^BrN0 3 Calculated: C 54.25; H 5.69; N 3.95 Found: C 54.05; H, 5.55; N 3.81

This connection is referred to below as connection 140.

Example XIV

Preparation of ethyl 2- (4-bromo-2-methylphenylaminocarbonyl) butanoate

Ethyl 2- (chlorocarbonyl) butanoate (5.8 g, 0.03 mol), 4-bromo-2-methylaniline (5.0 g, 0.03 mol) and triethylamine (3.27 g, 0.03 mol) described under the same conditions as in example I reacted to give 7.4 g (0.02 mol) of ethyl 2- (4-bromo-2-methylphenylaminocarbonyl) butanoate as a white solid having a melting point of 98 ⁰ C to 100 ⁰ C * The elemental analysis of the product gave the following:

Analysis: ^c i4 ^H i8 ^BrN0 3 Calculated: C 51.23; H 5.53; N 4,27 Found: C 51.40; H 5.63; N 4,25

This connection will be referred to as connection 141 in the following.

Example XV

In the same manner as in Example XIV, the further compounds were prepared. The structures and analysis values of compounds 142 to 152 are listed in the following Table G.

Table G Representative malonic acid derivative compounds

^Y 2 ²

^Y 3 ³

^R 5 °

C-C-C

I '

- NH -

substituents

Connection no.

Elemental Calculated Found

μ μ C H

-Egg-

melting

Mt 141 IM 14S 14t 141 14 «14T ITI Ш

• г »г • г» г • г

^СИ 1 СД

^£ S • г

CH, СИ, CH ₁

^см з сн,

M СИ.

с ₂ н _$

с ₂ н _$

_2-CH} -4-ar SI.4 "

г.э- <сіисмси.сн> - η. «

2-CHj-4-ir

с ₂ и _$

lS- « ₂ 2 ^ Η ₃ -4- · γ

4-С> И3 «. · $ 31.fi Sl.23 S3.« 4 4 ». W 4 · · · 2

. • г

.14

• і. * Г .г · .г · .г ·

.Sl .21

.и

1.12 4.2 «1.S» 4.1 «

1.И

1.М 4.21 1.М 4.4 «I.M

Sl. M II. U 40.11 41.24 M.M 3 ·. **

з ".м

Sl.4) S3. ·· 4 · .Μ

41.11

1·

.14 .S4 .SL -SS .14 .U .Sl

4.11

глг

1.8 '

І.в * 4.Tl 1.S2 4.41 •

IIS-II1 US Ill

βΙΙ

• II

Oil

• II

• II

• II

• II

inn · • η

Example XVI

Preparation of 3 - / (4-bromo-2-methylphenol) amino / -2-bromo-2-methyl-3-oxo-propanoic acid

An amount of 1.25 g (0.003 mol) of ethyl 3 - / (4-bromo-2-methylphenyl) amino / 2-bromo-2-methyl-3-oxo-propanoate prepared in Example XV (Compound 144) was added The potassium salt of the acid was then acidified with concentrated HCl and worked up in the same manner as described in Example VII to give 1.04 g (0.003 mol) of 3 - / (4-bromo-2-methylphenyl) amino / 2-bromo-2-methyl-3-oxopropanoic acid in the form of a white solid having a melting point of 133 ⁰ C to 136 ⁰ C * The NMR Analysis of the product indicated the following: NMR (COCl ₃ -OMSO d _β ): d ~ 2.05 (s, 3H), 2.20 (s, 3H), 2.4-2.6 (br s, H) , 7.2-7.53 (m, 3H), 9.6-9.8 (br s, H) ppm.

This connection is referred to below as connection 153 ·

Example XVII

Preparation of N-butyl 3 - / (4-bromo-2-methylphenyl) amino / 3-oxopropanamide

A mixture of 490 g (0.02 mol) of ethyl 3 - / (4-bromo-2-methylphenyl) amino / 3-oxo-propanoate prepared in Example I (Compound No. 75), 358 g (4.9 mol) N-Butylamine, 150 ml of ethanol and 5 drops of water were stirred at room temperature for about 16 hours. · After this period, rotary evaporation gave a crude product as a white solid. The white solid was recrystallized from ethyl acetate-hexane to give 3.08 g. 0.009 mole) of N-butyl 3 - / (4-bromo-2-methylphenyl) amino / -3-oxo-propanamide · gave Elemental analysis of the product having a melting point of 123 ⁰ C to 125 ° C as follows:

Analysis: ^C i4 ^H i9 ^BrN 2 ° 2 Calculated: C 51.38; H 5.85; N 8,56 Found: C 5l _f 42; H 5.91; N 8,69

This connection is referred to below as connection 154.

Example XVIII Preparation of ethyl 1-chlorocarbonylcyclopropanecarboxylate

In 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 and with cooling to a temperature of 0 C 50 g (0.27 mol Diethyl 1,1-cyclopropanedicarboxylate was added. The mixture was stirred at room temperature for about 16 hours. The solvent was removed under reduced pressure to give a white residue which was dissolved in water and extracted with ether. The water solution was acidified to pH 2 with 25% aqueous hydrochloric acid and the organic acid was washed with ethyl ether (4 400 ml) extracted from the aqueous suspension. The ether extract was dried over magnesium sulfate, the solvent was driven off under reduced pressure and the monocarboxylic acid resulted as a clear liquid. The clear liquid was dissolved in 300 ml of methylene chloride, then 74 g (0.62 mol) of thionyl chloride was added and the resulting mixture was heated at reflux for about 16 hours. The volatiles were removed under reduced pressure to give 45.7 g (0.25 mol) of ethyl 1-chlorocarbonyl cyclopropanecarboxylate. The NMR analysis of the product gave the following:

NMR _(CDCl3): / 1.22 to 1.50 (t, 3H). 1.75 (s, 4H), 4.1-4.52 (q, 2H) ppm.

This connection is referred to below as connection 155.

Example XIX Preparation of ethyl 1-chlorocarbonylcyclobutanecarboxylate

Diethyl 1, 1-cyclobutanedicarboxylate (20.0 g, 0.10 mol) was saponified with 6.59 g (0.10 mol) of potassium hydroxide in a mixture of 200 mL of ethanol and 1.80 g (0.10 mol) of water and worked up to give the monocarboxylic acid which was reacted with thionyl chloride (8.86 g, 0.07 mol) in methylene chloride solution as described in Example XVIII. Removal of the solvent gave 7.48 g (0.04 mol) of ethyl 1-chlorocarbonylcyclobutanecarboxylate. · NMR analysis of the product indicated the following:

NMR (COCl ₃ ): * 1.10-1.44 (t, 3H), 1.7-2.85 (in, 6H), 4.05-4.5 (q, 2H) ppm.

This connection will hereinafter be referred to as connection 156 ·

Example XX Preparation of ethyl 1-chlorocarbonylcyclopentanecarboxylate

In the same manner as in the procedure described in Example XVIII, except that the refluxing with thionyl chloride in methylene chloride was carried out for only 2 hours, an amount of 10 g (0.05 mol) of diethyl 1,1-cyclopentanedicarboxylate converted into 5.67 g (0.03 mol) of ethyl 1-chlorocarbonyl cyclopentanecarboxylate. NMR analysis of the product indicated the following: NMR (CDCl ₃ ): / 1.10-1.49 (t, 3H), 1.56- 2.48 (m, 8H), 4.0-4.5 (q, 2H) ppm.

This connection will hereinafter be referred to as connection 157.

Example XXI Preparation of ethyl Z-bromo-Z-chloro-carbonyl-propanoate

In the same manner as in the procedure described in Example XVIII, except that the refluxing with thionyl chloride in methylene chloride solution was carried out for only 6 hours and the solution was allowed to stand at room temperature for 16 hours, an amount of 25.0 g (0.10 mol) of diethyl 2-bromo-2-methylmalonate converted to 12.94 g (0.05 mol) of ethyl г-Ьгот-г-спіог-сагЬопуіргорапоаі · This compound was used for the preparation of compounds No. 144 to and 152 used in Example XV · The NMR analysis of the product gave the following:

NMR (CDCl ₃ ): I 1.10-147 (t, 3H), 2.05-2.17 (s pair, 3H), 4.05-4.55 (q pair, 2H) ppm.

This connection is referred to below as connection 158 ·

Example XXII Preparation of ethyl 3 - / (4-chlorophenyl) amino / 3-oxopropanoate

4-Chloroaniline (25.4 g, 0.20 mol) and diethyl malonate (48 g, 0.30 mol) were prepared in the same manner as that of AK, Sen and P. Sengupta, Oour. Indian Chem. Soc. 46 (9), 857-859 (1969). The reaction yielded a greenish solid which was recrystallized from toluene-hexane (1: 1) followed by isopropyl ether, and 9.0 g (0.04 mol) of ethyl 3 - / (4-chlorophenyl) amino / 3-oxopropanoate as gave white crystals with a melting point of 82 ⁰ C to 83 ⁰ C · The elemental analysis of the product gave the following:

Analysis: ^C ll ^H 12 ^ClN0 3 Calculated: C 54.67; H, 5.01; N 5.80 Found: C 54.90; H 4,94; N 6.07

This connection will hereinafter be referred to as connection 159.

-88-

Example XXIII

Preparation of ethyl 3 - / (4-methylthiozol-2-yl) amino / 3-oxo- propanoate

In the same procedure as in the procedure described in Веізріеі I, 2-amino-4-methylthiozole was reacted with ethylmalonyl chloride using triethylamine as the acid acceptor in tetrahydrofuran solution. The product ethyl 3 - / (4-methylthiazol-2-yl ) amino / -3-oxopropanoate (7.5 g, 0.03 mol) was recovered as off-white Peststoff having a melting point of 138 to 141 ⁰ g ° C. The elemental analysis of the product gave the following:

Analysis: G ₉ H ₁₂ II ₂ OS Calculated: G 47.36; H 5.30; TS 12,27

Found: G 47.50; H 4.62; K 11,77

This compound is hereinafter referred to as compound I6O.

Example XXIV

In the same manner and in the same way as described in Example XXIII, the further compounds were prepared. The structures and analysis values of the compounds I6I to are listed in Table H below.

Table H Representative malonic acid derivative compounds

il

₀ Second

connection Elemental analysis of enamel · ZZZZ Found point

Cl

4t.2S

3.21 »« 1 * 4 - «* l

4.14 · - «Μ ·« ·

·· « ^{IM IM}

ul

 CH,

(dec.) »(with decomposition)

Table H (cont.) Representative malonic acid derivative compounds

0 0

U Il

H ₅ C 0-C-CH ₂ C-NH-R ^

Connection Nr,

US

IN THE

CH,

Elemental analysis

Calculated

HN

Found

HN

Enamel · 42imkt

S ·. «4 $ .10 13.2 · SO.U S.IS 13.31 111-131

41.H P.30 12.21 41.41 S.4t 11.H »« - »2

Ul32.Ϊ · 3.0 »f.» 32.H 2.34

143-US

IU

»и

4t.M 4.SI II.S4 4 ».Э0 4.Sl II.S4

Table H (Forte.) Representative malonic acid derivative compounds

0 0 HcC ₀ OC-CH ₀ -C-NH-R;

Э ^ ί D

connection Elemental Analysis

enamel

Calculated

Found

UO

wl

112

et

Cl

".si

U.4I 4.10 U.31 «» ··

^{ии пт}

«* · *« IM-IM

SZ. «S.H 4

Sl.01 ill * "

\: J 1.II-1.4S (tM). 2.20 (lW). ijfc (t.lH), 1.4k ($ .210. 4.01-4.4 · (Ч.2И). iM (S.И). Ϊ.Ο I «.N), f.Ob-t.SI (br І .ИІРИ.

IM-121

Example XXV Preparation of ethyl 2-chlorocarbonyl-3-methyl-2-butenoate

Diethyl isopropylidene malonate (30 g, O, IS mole) was saponified with 10.0 g (0.15 mole) potassium hydroxide in 200 mL ethanol solution and worked up to give monocarboxylic acid, which was then treated with thionyl chloride (10 mL, 0.1 mol) in Methylene chloride solution in the same manner as that described in Example XVIII. Removal of the solvent gave 9.6 g (0.05 mol) of ethyl гІ-сІііогоагЬопуі-З-теіпуі-г-butenoate. · NMR analysis of the residual product in CDCl ₃ solution showed complete conversion of the carboxylic acid to the acid chloride, such as proved by the absence of a subfield carboxylic acid proton.

The connection is referred to below as connection 174 · Example XXVI.

Preparation of ethyl 2 - / (4-bromo-2-methylphenyl) aminocarbonyl / 3-methyl-2-butenoate

In the same manner as described in the procedure in Example I, ethyl 2-chlorocarbonyl-3-raethyl-2-butenoate prepared in Example XXV (9.6 g, 0.05 mol), 4-bromo-2-methylaniline ( 5.3 g, 0.03 mol) and triethylamine (4.0 mL, 0.03 mol) to 2.9 g (0.009 mol) ethyl 2 - / (4-bromo-2-raethylphenyl) aminocarbonyl / -3- reacted methyl-2-butenoate in the form of a white solid having a melting point of 116 ⁰ C to 119 ⁰ C. The NMR analysis of the product gave the following:

NMR (CDCl ₃ ): S 1.17-1.43 (t, 3H). 2.10-2.19 (d, 6H), 2.28 (s.3H), 4.08-4.50 (q, 2H), 7.21-8.20 (m, 4H) ppm.

This connection will be referred to as connection 175 below. Example XXVII Preparation of 3,4-dichloro ^ 5-dimethvlaniline

A solution of 5.0 g (0.03 mol) of 3,4-oichloro-2,5-dimethyl-nitrobenzene in 70 ml of ethanol was used at room temperature and 50 psi in the presence of 0.25 g of 10% palladium on charcoal Catalyst hydrogenated · The workup of the reaction mixture gave 1.21 g (0.006 mol) of 3,4-dichloro-2,5-dimethylaniline in the form of a yellow solid having a melting point of 72 ⁰ C to 76 ⁰ C. The NMR analysis of the product gave the following : NMR (COCl _3): ^ 2.24 (s, 3H), 2.32 (s, 3H). 3.60 (br s, 2H), 6.50 (s, H) ppm ·

This connection is referred to below as connection 176 ·

Example XXVIII Preparation of 4,5-dichloro-2-methoxvaniline

Part A; Preparation of 2,2-dimethy-N- (4-chloro-2-methoxyphenyl) propanamide

Into a stirred solution containing 10.0 g (0.06 mol) of 4-chloro-2-methoxyaniline and 6.42 g (0.06 mol) of triethylamine in 200 mL of tetrahydrofuran were added 7.65 g (0.06 g) The resulting mixture was stirred at room temperature for two hours. Triethylamine hydrochloride was precipitated and filtered off and the filtrate was freed from the solvent under vacuum to give a dark liquid, which was taken up in methylene chloride The solution was washed with 2N HCl (2 × 100 ml) and then with water (1 × 100 ml), dried over magnesium sulfate, and the solvent was evaporated to give a crude product, which was crystallized from hexane to give 6.82 g (0 , 03 mol) of 2,2-dimethyl-N- (4-chloro-2-methoxyphenyl) propanamide were used as a

won first and second yield. The NMR analysis of the product gave the following:

NMR _(CDCl3): <T 1.32 (a 9H.). 3.91 (s, 3H), 6.83-7.08 (m, 2H), 8.28-8.52 (d 2H) ppm.

Part B: Preparation of 2,2-dimethyl-N- (4,5-dichloro-2-methoxyphenyl) propanamide

Into a stirred solution containing 6.82 g (0.03 mol) of 2,2-dimethyl-N- (4-chloro-2-methoxyphenyl) propanamide prepared in Part A in 150 ml of chloroform were added 3, Over a period of 40 minutes, 81 g (0.03 mol) of sulfuryl chloride were added. The resulting mixture was refluxed for 3 days with the mixture being cooled each day and an additional 3.81 g (0.03 mol) of sulfuryl chloride added After refluxing for 3 days, thin layer chromatography of the mixture indicated that the reaction was complete. The volatiles were removed from the reaction mixture and 3.70 g (0.01 mol) of 2,2-dimethyl-N- (4,5-dichloro-2-methoxyphenyl) -propanamide was purified by flash column chromatography eluting with dichloromethane of a bright yellow-orange solid · The NMR analysis of this product gave the following:

NMR _(CDCl3): T1,34 (s, 9H), 3.92 (s, 3H), 6.94 (s, H), 8.08 (br s H), 8.67 (s, H) ppm.

Part C: Preparation of 4,5-dichloro-2-methoxyaniline

The 2,2-dimethyl-N- (4,5-dichloro-2-methoxyphenyl) propanamide prepared in Part B (3.70 g, 0.01 mol) was dissolved in ethanol: 12N HCl (1: 1), the Mixture was heated under reflux overnight and then freed from the volatiles by means of rotary evaporator. Partitioning between 2N HCl and dichloromethane gave an acid soluble fraction which was worked up to give 1.1 g (0.01 mol) of pure 4,5-dichloro-2-methoxy-aniline as determined by thin layer chromatography. The abovementioned dichloromethane fraction was freed from the solvent and gave an

C., which was refluxed overnight with ethanol: 12N HCl, and additionally provided 1.2 g (0.01 mol) of pure 4,5-dichloro-2-methoxy-aniline, as determined by thin layer chromatography. The NMR analysis of the product gave the following:

NMR _(CDCl3): X 3.88 (s, 5H), 6.73 to 6.90 (d, 2H) ppm.

This connection is referred to below as connection 177.

Example XXIX

Preparation of 1- (4-bromo-2-methylphenvlaminocarbonyl) cvclobutanecarboxylic acid

An amount of 3.0 g (0.009 mol) of ethyl 1- (4-bromo-2-methylphenylaminocarbonyl) cyclobutanecarboxylate prepared in Example IX (Compound 129) was hydrolyzed by 2.19 g in the same manner as described in Example XI (0.007 mol) of 1- (4-bromo-2-methylphenylaminocarbonyl) cyclobutanecarboxylic acid, Compound 181, with a melting point of 154 ⁰ C to 155 ⁰ C to win.

Example XXX Preparation of ethyl (chlorocarbonylmethoxyacetate Part A; Preparation of diethyl methoxymalonate

A mixture of 50.4 g (0.3 mol) of oimethylmethoxymalonate, para-toluenesulfonic acid (2.76 g) and 300 ml of ethanol was refluxed for about 24 hours. The volatiles were then removed under reduced pressure, with stirring Water bath of about 25 ^° C. A second amount of 300 ml of ethanol was added and the mixture was then refluxed for about 5 hours, after which it was stirred for about 64 hours at room temperature Removal of ethanol from the mixture under reduced pressure gave 61.0 g (0.3 mol) of diethyl methoxymalonate, which was used in subsequent steps without further purification.

Part B: Preparation of Mono-Ethyl Methoxymalonate

A mixture of 30.0 g (0.2 mol) of diethyl methoxymalonate (part A, above), 8.85 g (0.2 mol) of potassium hydroxide, 2.84 g (0.2 mol) of water and 300 ml of ethanol became 72 Stirred for hours at room temperature, after which the volatiles were removed under reduced pressure. The residue was dissolved in water and the pH of the solution was adjusted to 10 by the addition of potassium hydroxide. The solution was saturated with potassium chloride and extracted with methylene chloride (3 × 100 ml) to remove the unsaponified oyster. Acidification to pH = 1 and continuous extraction with methylene chloride gave 9.45 g (0.06 mol) of mono-ethyl methoxymalonate as a liquid.

Part C: Preparation of ethyl (chlorocarbonyl) methoxyacetate

A mixture of 5.88 g (0.04 mol) of mono-ethyl methoxymalonate from Part B, above, 8.63 g (0.07 mol) of thionyl chloride and 150 ml of methylene chloride was stirred for about 17 hours and then freed from the volatiles. When the NMR observation indicated that the reaction was not completed, the above-mentioned thxonyl chloride treatment in methylene chloride was repeated for a period of 65 hours. A third treatment with 8.63 g of thionyl chloride in 150 ml of methylene chloride was finally carried out, with refluxing for a period of about 7 hours. Removal of the volatiles under reduced pressure gave 6.0 g (0.03 mol) of ethyl (chlorocarbonyl) methoxyacetate, Compound 211. The NMR analysis of the product indicated the following:

Ή NMR (CDCl ₃ ): <T 1.16-1.53 (t, 3H, CH ₃ ), 3.58 (s, 3H, CH ₃ O), 4.13-4.56 (q, 2H, CH ₂ ) 4.62 (s, H, CH) ppm.

Seismic Example XXXI

Preparation of Ethyl 3 - / (3 _t 5-dichlorophenyl) amino / 2-methoxy " 3-oxopropanoate

3.5 Dichloroaniline (2.69 g, 0.02 mol) and ethyl (chlorocarbonyl) methoxyacetate (3.0 g, 0.02 mol) prepared in Example LIII (Compound 211) were dissolved in the presence of triethylamine (1, 68 g, 0.02 mol) in 200 ml of methylene chloride in the same manner as described in Example I to give 1.34 g (0.004 mol) of ethyl 3- / (3,5-dichlorophenyl) amino / 2- methoxy-3-oxopropanoate, compound 213, gain having a melting point of 89.5 to 92.5 C ^{0 0} C ·

Example XXXII Preparation of mono-methyl methoxymalonate

Oimethylmethoxymalonate (50.0 g, 0.3 mol) was treated with potassium hydroxide (17.3 g, 0.3 mol) in a mixture of 500 ml of methanol and 5.55 g (0.3 mol) of water according to the general procedure of Example VII, but using a reaction time of about 16 hours, saponified. The reaction mixture was freed of solvents and the residue was dissolved in water and extracted twice with ether to remove the unreacted diester. The aqueous layer was then saturated with potassium chloride, acidified with 2H HCl and extracted twice with ethyl ether. Since only a small amount of the product could be recovered by this method, the aqueous phase was subjected to continuous liquid-liquid extraction with methylene chloride three times for 16 hours, adjusting the pH from 4 to 1 at the beginning of the second extraction. The work-up of the combined extracts afforded 29.24 g (0.2 mol) of mono-methyl methoxymalonate, Compound 214. The NMR analysis of the product indicated the following:

¹ H NMR (COCl _3): ¥ 3.54 (s, 3H, alpha CH ₃ O), 3.86 (s, 3H, ester CH ₃ O), 4.51 (s, H, CH), 9, 36 (s, H, CO ₂ H) ppm.

Example XXXIII

Preparation of methyl 3 - / (4-bromo-2-fluorophenyl) amino / -2-methoxy-3-oxopropanoate

To a stirred mixture of 2.78 g (0.02 mole) of mono-methyl methoxymalonate prepared in Example LVI (Compound 214) and 3.56 g (0.02 mole) of 4-bromo-2-fluoroaniline in about 100 parts A dry solution of 3.87 g (0.02 mol) of 1-S-dicyclohexylcarbodiimide in about 30 ml of dry tetrahydrofuran was added dropwise to dry tetrahydrofuran while the reaction mixture was cooled in an ice-water bath. The reaction mixture was then allowed to warm slowly to room temperature stirring continued for a period of about 65 hours. Oas precipitated byproduct 1,3-dicyclohexylurea (3.15 g) was removed by filtration, the filtrate evaporated in vacuo, and the residue dissolved in methylene chloride. This solution was washed with dilute HCl and then extracted with water, then dried (MgSO 4) and the solvent was evaporated in vacuo; a colorless liquid resulted. Flash column chromatography of this liquid on silica gel eluting with hexane-ethyl acetate (7: 3) gave after work-up a liquid which crystallized on standing. Recrystallization from hexane containing a small amount of ethyl acetate gave 2.3 g (0, 01 mol) of methyl 3 - / (4-Brora-2-fluorophenyl) amino / -2-methoxy-3-oxopropanoate, compound 215, having a melting temperature of 51 ⁰ C to 53 ⁰ C.

Example XXXIV

In the same manner as in Example XXXIII, the further compounds were prepared. The structures and analysis values of compounds 216 to 219 are listed in the following Table I.

Table I Representative malonic acid derivative compounds

OCH,

CH ₃ O

C-C-C-NH O δ

^z io

2U substituent 3.4-Cl ₂ Calculated C Elamentaranalvse H 3:45 N 4.80 C 45.21 Found 3.91 N 4.20 enamel connection 217 4o 4-CF ₃ 45.23 4.15 4.81 49.88 H 4.29 4.91 Point No. 211 4-Br 49.49 4:00 - 43.73 4:04 - ° C 219 3.4.5-Cl ₃ 43.73 3:09 40.44 3.22 78-81 40.46 101-103 55-59 117-121

100

Example XXXV

Preparation of t-butyl 3-i. (3,5-dichlorophenyl) amino 3-2-methoxy -3-oxopropanoate

Part A: Preparation of t-butyl methyl methoxymalonate

Into a stirred solution of 9.26 g (0.06 mol) of methyl (chlorocarbonyl) methoxyacetate in 25 ml of carbon tetrachloride was added a slurry of 4.94 g (0.07 mol) of anhydrous t-butyl alcohol, 4.50 ml (0, 06 mol) of pyridine and 25 ml of carbon tetrachloride over a period of 20 minutes and with cooling to 0 ⁰ C to 5 ⁰ C through an ice bath. Upon completion of the addition, the cooling bath was removed and the mixture was stirred for 4 hours at ambient temperature, after which the pyridine hydrochloride was removed from the mixture by filtering. The filtrate was diluted with ml of methylene chloride and partitioned with 100 ml of saturated aqueous sodium bicarbonate, then the organic phase was extracted with cold 10% hydrochloric acid (3 × 100 ml), then cold water (3 × 100 ml) and then dried (MgSO ₄ ) has been; the solvents were evaporated. The residue was vacuum distilled to give 7.57 g (0.04 mol) of t-butyl methylmethoxymalonat having a boiling point of 93.5 ⁰ C to 95 ⁰ C at 4.0 mm Hg.

Part B; Preparation of Mono-t-butylmethoxyroalonate

T-Butylmethyl methoxymalonate (7.57 g, 0.04 mol) prepared in Part A was post-added with potassium hydroxide (2.45 g, 0.04 mol) in a mixture of 25 ml of methanol and 668 microliters (0.04 mol) of water saponified according to the general procedure of Example VII, but with a reaction time of 20 hours was observed. Work-up by the general method of Example VII gave 5.42 g (0.03 mol) of mono-t-butylmethoxymalonate. The NMR analysis of the product gave the following:

101

¹ H NMR (CDCl ₃ ): 1,4 1.45 (s, 9H-t-butyl), 3.58 (s, 3H, CH ₃ O), 4.45 (s, H, CH), 10.51 ( s, H, CO ₂ H) ppm.

Part C: Preparation of t-butyl 3-f (3,5-dichlorophenyl) amino 7-2-methoxy-3-oxopropanoate

Mono-t-butylmethoxymalonate (5.42 g, 0.03 mol), 3,5-dichloroaniline (4.62 g, 0.03 mol) and 1,3-dicyclohexylcarbodiimide (5.88 g, 0 , 03 mol) were reacted in the same manner as described in Example LVII to give 2.92 g (0.009 mol) of t-butyl 3-f (3,5-dichlorophenyl) amino-2-methoxy-3-oxopropanoate a melting point of 129.5 ⁰ C to 131.5 ⁰ C.

Example XXXVI

Preparation of methyl 3-f (3,5-dichlorophenyl) amino] -2-methoxy-3-thioxopropanoate

A slurry of 3.5 g (0.01 mol) of methyl 3- (3,5-dichlorophenyl) amino] -2-methoxy-3-oxo-propanoate (Compound 233, example LXX), 2.42 g (0.006 mol) 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,4-disulphide and 35 ml of anhydrous 1,1-dimethoxyethane were stirred at room temperature for a period of about 20 hours, and Stirring was then continued at 55 ^° C and with tests over a period of 168 hours. The solvent was removed from the reaction mixture under reduced pressure and the residue was worked up by flash column chromatography to give 2.31 g (0.007 mol) of methyl 3- [(3,5-dichloro-phenyl) -amino] -2-methoxy. 3-thioxopropanoate, compound 238, having a melting point of 144 ⁰ C to 147 ⁰ C won.

Example XXXVII

Preparation of 2-cyclopropenyl-1-carboethoxy-1-N- (2-methyl-4-bromophenyl) 3-carboxamide

Part A; Preparation of diethyl bis (2,3-trimethylsilyl) cyclopropene 1,1-dicarboxylate

A 50 ml round bottom flask was equipped with a magnetic stir bar and a reflux condenser with N 2 inlet. The flask was charged with 183.0 g (1.07 mol) of bis (trimethylsilyl) acetylene and 0.40 g (0.0015 mol) of copper (II) acetylacetonate. With the aid of an oil bath, the temperature of the stirred mixture was raised to 145 ⁰ C. By means of a syringe pump 39.3 g (0.21 mol) Oiethyldiazomalonat were added over a period of 36 hours. After all Oiazomalonat had been added, was heated for another 12 hours at 145 ⁰ C. The excess bis (tri-methylsilyl) acetylene was removed by vacuum distillation. The residue product was purified by flash column chromatography eluting with 80:20 hexane-ethyl acetate to give 17.0 g (0.05 mol) of diethyl bis (2,3-trimethylsilyl) -cyclopropene-1,1-dicarboxylate as a yellow liquid. The NMR analysis of the product gave the following:

¹ H NMR (CDCl _3): c / o, 23 (s, 18H), 1.20 (t, 6H), 4.17 (q, 4H) ppm

Part B: Preparation of diethylcyclopropene 1,1-dicarboxylate

A 500 ml round bottom flask was equipped with magnetic stir bar and N inlet. The flask was charged with 21.0 g (0.07 mol) of diethyl bis (2,3-trimethylsilyl) cyclopropene 1,1-dicarboxylate, 125 ml of acetonitrile, 12.2 g (0.21 mol) of anhydrous KF, and 6, 50 g (0.02 mol) of Oicyclohexano-lS-crown-ö-ether filled. The mixture was stirred for 6 hours at room temperature. The GE-

103

The mixture was filtered and the filtrate was concentrated under reduced pressure to a deep red Dl. This Dl was taken up in 100 ml of methanol and stirred for 24 hours at room temperature. The methanol was removed in vacuo and the residue was purified by flash column chromatography to give 6.25 g (0.02 mol) of diethylcyclopropene 1,1-dicarboxylate as a yellow Dl. NMR analysis of the product indicated the following:

¹ H NMR _(CDCl3): 0 ^ 1.25 (t, 6H), 4.23 (q, 4H); 7.08 (s, 2H)

Part C: Preparation of mono-ethylcyclopropene 1,1-dicarboxylate

A 250 ml round bottom flask was equipped with a magnetic stir bar and an additional funnel with Np inlet. The flask was charged with 6.15 g (0.03 mol) of diethylcyclopropene 1,1-dicarboxylate and 50 ml of ethanol. The stirred mixture was cooled in an ice bath and a solution of 1.33 g (0.03 mol) of NaOH in 5.0 ml of water was added dropwise. Then the mixture was allowed to warm to room temperature and stirred for 3 days. The reaction mixture was concentrated under reduced pressure to 1/4 of its original volume, diluted with ice-water and extracted twice with ether. The basic aqueous phase was acidified with ice-cold TO% HCl and extracted three times with ethyl acetate. The ethyl acetate was dried (MgSO 4) and the solvent was removed under reduced pressure to leave an orange solid. This was recrystallized from hexane-ethyl acetate to give 3.65 g (0.02 mol) of mono-ethylcyclopropene-1,1- dicarboxylate in the form of a light yellow solid having a melting point of 76.0 ⁰ C to 77.5 ⁰ C. The NMR analysis of the product gave the following:

¹ H NMR (CDCl ₃ ): cT 1.20 (t, 3H), 4.25 (q, 2H), 6.80 (s, 2H), 11.5 (br s, IH) ppm.

104

Part D: Preparation of 1-Carboethoxy-1-ethoxycarbonyloxycarbonyl-2-cyclopropene

A 250 ml round bottom flask was equipped with a magnetic stir bar and an additional N ₂ inlet funnel. The flask was charged with 1.3 g (0.008 mol) of mono-ethylcyclopropene-1,1-dicarboxylate, 50 ml of dry THF, 2.3 g (0.02 mol) of potassium carbonate (anhydrous) and 450 mg of dicyclohexano-er-crown- ö ether filled. The stirred reaction mixture was cooled to 0 ^° C. and 0.90 g (0.008 mole) of ethyl chloroformate in 10 ml of THF was added dropwise. The mixture was stirred at ⁰ C for 2.5 hours. At this time, an aliquot of the reaction mixture at 1820 cm "in the infrared showed very strong anhydride carbonyl extension, indicating the formation of mixed anhydride 1-carboethoxy-1-ethoxycarbonyloxycarbonyl-2-cyclopropene Part E continues to be used.

Part E; Preparation of 2-cyclopropenyl-1-carboethoxy-1-CN- (2-methyl-4-bromophenyl) -1-carboxamide

A solution of 1.40 g (0.0075 mole) of 2-methyl-4-bromoaniline in 10 mL of tetrahydrofuran was added at 0 ⁰ C was added dropwise into the reaction mixture of Part D. The mixture was allowed to warm to room temperature and stirred for 2 hours. The reaction mixture was filtered and the filtrate was concentrated under reduced pressure; an orange solid was recovered. This solid was washed with ether and recrystallized from hexane-ethyl acetate to give 1.5 g (0.004 mol) of 2-cyclopropenyl-1-carboethoxy-1-CN- (2-methyl-4-bromophenyl) J carboxamide. Compound 256, recovered in the form of a white crystalline solid having a melting point of 151 ⁰ C to 153 ⁰ C.

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Зеізріеі XZZVIII

'effective representative LIalonsäurederivatverbindungen on the delay of the PfIanzenwachsturns - Green beans and' zen .Yei

Solutions of the test compounds listed in Table I below were prepared by dissolving 68.3 mg of the corresponding compound in 5.5 ml of acetone and then making up to the final volume of 11.0 ml of water. When the solution was turbid when the solution was added to the solution, the use of V / asser was discontinued and acetone Ьіз added to the final volume of 11.0 ml. The resulting stock solutions contained 6255 parts by mass per million of the corresponding compound. The test concentration in parts of the test compound per Ilillion parts of the final solution used in the plant growth delay tests of Table I was obtained by suitable dilutions of the stock suspension with acetone and water (50/50 v / v).

Seeds of green beans, wheat, honey, cucumber, sunflower, flax.3, buckwheat, tomato, interhart rye, marigold, soybeans, millet, vealgrass and peas were grown in sandy loam soil in a dish with the following dimensions: 3.5 inches (88.9 mm) wide χ 7.9 inches (100.66 mm) long χ 1.0 inches (25.4 mm) high. Twelve to fourteen days after plugging, at the time the bean's first trifoliolate leaf was at least 3 inches long, each concentration of the test compounds listed in Table I as a foliar spray was reduced to 10 psig (0.703 at Aspirated sprayer (all dishes were sprayed at a tight 4 pounds per acre (4.4S kg / ha)). As a control, a water-acetone solution containing no test compound was also applied to a Shell sprayed. After drying, all planters were placed in a greenhouse at a temperature of GO ⁰ P + _ 5 ° P and (24,4 ⁰ G)

106

Humidity of 50 % + 5 % . Ten to 14 days after treatment, visual signs of plant delay efficacy were observed.

The visual observations of growth delay were recorded using a numerical rating system. The numerical scores from "O" to "10" were used to indicate the degree of effectiveness of the growth delay observed in comparison to the untreated control. A rating of "0" shows no visible response, a rating of "5" shows a 50% growth delay compared to the control and a "10" shows a 100 % ± 10 % growth delay compared to the control. In other words, this means that a "5" indicates that the increase in plant growth is only half that of the control or that the plant has grown by only half in comparison to the control. This rating system indicates any delay in plant height compared to the untreated control. The results are listed in Table I.

107

Table I

Effect of representative Malonsäurederivatverbindunqen on the delay of plant growth - green beans

Connection No. Evaluation of the growth delay

Control 0

1 2

2 4 5 7

10 2

11 7

13 2

14 2

15 4 18 1

20 2

21 6

22 9

25 6

26 4

28 6

29 2

30 2

33 2

34 6

35 8

36 2

37 5

38 5 40 3 43 2

Table I (cont.)

Effect of Representative Malonic Acid Derivative Compounds on Delaying Plant Growth - Green Beans

Connection No. Evaluation of the growth delay

44 2

2

46 9

47 2

3

50 3

51 3

57 6

58 4 63 2

66 5

67 2

2

5 5

71 2

2

6

2

79 5

80 2

81 2

82 3

83 2

84 4

85 2

2

Table I (cont.)

Effect of Representative Malonic Acid Derivative Compounds on Delaying Plant Growth - Green Beans

Connection Nr «Evaluation of the growth delay

87 2

88 3 90 2 92 4

94 2

95 3

98 3

99 4

100 3

101 2

102 7

104 2

105 3

107 3

108 2

110 4

111 9

112 3

114 4

115 3

116 7

117 2

118 2

120 2

121 4

122 4

Table I (Forts »)

Effect of Representative Malonic Acid Derivative Compounds on Delaying Plant Growth - Green Beans

Connection No. Evaluation of the growth delay

123 3

125 5

126 4

128 2

129 5 135 3

140 3

141 1

144 6

145 4

146 3

147 4

148 5

149 3

150 1

151 3

153 3

154 2 159 4 168 1 173 2 175 4

Ill

Table I (Forts)

Effect of Representative Malonic Acid Derivative Compounds on Plant Growth Delay - Green Beans

Connection No. Evaluation of the growth delay

212 2

213 8 216 3

218 3

219 2

222 2

223 2

224 4 226 2 228 2

232 2

233 6

234 IO

235 8

236 8

237 2

Table I

Effect of Representative Malonic Acid Derivative Compounds on Plant Growth Delay - Wheat

Connection No. Evaluation of the growth delay

Control 0

22 1

46 2

3

82 2

84 2

88 2

92 3

107 2

110 2

111 3

114 4

115 5

2

117 2

121 2

2

123 2

125 2

126 2 129 2

144 3

145 3

2

113

Table I (cont.)

Effect of representative Malonsäurederivatverbindunqen on the delay of plant growth - wheat

Connection No. Evaluation of the VVuchsverzöqerunq

212 1

213 7 216 3

218 2

219 5 224 2

233 5

234 6

235 5

236 5

237 4

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The results in Table I show that the treatment of the plants with certain lalonic acid derivative compounds allows a significant delay of plant growth in comparison with the untreated control plants.

Example ΣΣΣΙΧ

Effect of Representative Malonic Acid Derivative Compounds on Delay: Plant Growth - Wheat

Solutions of the test compounds listed in Table I were prepared by dissolving the compounds in acetone / water (50/50 v / v) containing 0.05 % v / v Triton X-100 surfactant. As described in detail below, these test compound solutions were applied to wheat at a concentration of 0.5 pounds of active ingredient per acre or 1.0 pound of active ingredient per acre.

Wheat seeds were placed in sandy loam in a tray of the following dimensions: 3 "5 inches (88.9 mm) wide χ 7.9 inches (100.66 mm) long χ 1.0 inch (24.5 mm) high. Eight days after emergence in the 2-3-leaf stage of wheat, each concentration of the test compounds listed in Table J was applied to a tray as a foliar spray using an aspirator set at 10 psig (0.703 atm.) Air pressure (all dishes were volumeed Sprayed 120 gallons per acre (508.7 l / ha)). As a control, a water-acetone solution containing no test compound was also sprayed on a dish. ITach drying, all seed trays were placed in a greenhouse at a temperature of 30 F + 5 ^{0 0} F (24.4 ⁰ C) and a humidity of 50% + 5 £ provided. 14 days after the treatment, visual similarities were found for the efficacy of plant growth retardation.

115

The visual observations of growth delay were recorded using a percentage rating system. These percentages from 0 to 100 were used to characterize the degree of efficacy of the growth delay observed in comparison to the untreated control. A rating of 0 % shows no visible reaction, a 50 % rating indicates that the growth increase of the wheat is only half that of the control plant or that the wheat has only grown by half compared to the control plant and a rating of 100 % % indicates maximum response. This rating system indicates any delay in wheat height compared to the untreated control plant. The results are listed in Table K ·

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Table K

Effect of Representative Malonic Acid Derivative Compounds on the Delay: of Pfi an ze nwa cha turn a - 'wheat

connection Mr. Ilenge s / acre) Percentage 'towel' 0 (Pound kg / ha ѵеггодегшія 30 control - 0.56 40 connection 96 0.5 1.12 60 1.0 0.56  70 connection 111 0.5 1.12 20 1.0 0.56 30 connection 114 0.5 1.12 10 1.0 0.56 10 connection 82 0.5 1.12 30 1.0 0.56 40 connection 115 0.5 1.12 40 1.0 0.56 70 connection 116 0.5 1.12 50 1.0 0.56 60 connection 117 0.5 1.12 1.0

The results in Table K show that treatment of the yeast with certain bluesone derivatives allows a significant retardation of plant matter compared to the untreated 7 / egg control group.

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Веізріеі 2

Y / irkuiig of representative LIalon3äurederivatverbindungen on the delay of plant growth - red maple and sycamore

Solutions of the test compounds listed in Table K were prepared by dissolving the compounds in acetone / Y / aaser (50/50 v / v) containing 0.1 % v / v Triton X-100 surfactant vial will be described in detail below, these solutions of the test compounds were applied to red maple and sycamore in a concentration of 1.0, 2.0 or 4.0 pounds of active ingredient per acre.

Red maple ( Acer rub rum ) and plane tree ( Platanus occidentalis ) seedlings were commercially obtained and grown in a gallon plastic container in sandy loam soil. The seedlings were kept in the greenhouse at a temperature of SO ⁰ F + 5 ° F and a humidity of 50 + 5 % . After a period of one month, the excess buds were removed from the developing trees to a dominant main shoot of 4 inches in length. At this time, each concentration of the test compounds listed in Table K was applied as a foliar spray to the individual trees using an aspiration sprayer set at 10 psig air pressure (all trees were injected with a volume of 120 gallons per acre). As a control, a water / acetone solution containing no test compound was also sprayed on certain trees. After drying, the trees were returned to the greenhouse for one month. Then (ie, a post-treatment gel) the visual signs of the effectiveness of the opening were observed and recorded.

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The percentage retardation of shoot length vigor in Table L was determined by the corresponding measurement of the tegіеЬез of each tree in comparison with the untreated control. The average length of the ТгіеЬез of the untreated control trees was 48 cm and 53 cm at the plane tree. The results in Table L represent the average values of 3 V / repeat measurements.

Table L

Effect of Representative Blalonic Acid Derivative Compounds on Delaying Plant Growth - Red maple and sycamore

Connection Hr. LIenge (pounds per Acre) Percentage deceleration d TrieblänsenvTachstums Rotahorn Sycamore 0 control - kg / ha 0 15 Connection 96 1.0 1.12 34 16 2.0 2.24 40 20 4.0 4.48 43 77 Connection 111 1.0 1.12 76 84 2.0 2.24 97 88 4.0 4.48 97

The results in Table L show that the treatment of red maple and sycamore with certain malonic acid derivative compounds gives a significant growth delay compared to untreated controls of rotahron and sycamore.

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TT T

Example ZLj.

Reproduction of Representative Malonic Acid Derivative Compounds on Retardation of Plant Growth ^ - Red maple and sycamore

Solutions of the test compounds listed in Table M were prepared by mixing the compounds were dissolved in acetone / '.Yasser (50:50 volume / volume) containing 0.1 To v / v dea surfactant Triton. As shown in detail below, these solutions of the test compounds were applied to red maple and sycamore at a concentration of 1.0 or 2.0 pounds per hectare per acre,

Seedlings with bare root of red maple (Acer rubrum) and sycamore ( Platanus occidentalis ) were obtained commercially and placed in a gallon plastic containers in sandy loam soil. The seedlings were grown in the greenhouse at a temperature of 80 ⁰ P + 5 ° 3? and a humidity of 50 + 5 7q . After a period of three months, the developing trees were cut back to half their height. Twenty-four hours after blending, each concentration of test compound listed in Table M was sprayed onto the individual trees as a foliar spray using an aspiration sprayer set at 10 psig air pressure (all trees were injected at a volume of 120 gallons per acre). As a control, a water / acetone solution containing no test compound was also sprayed on certain trees. ITaeh. After drying, all trees were returned to the greenhouse for a period of 45 days. After this time (ie, 45 days after the treatment), the visual signs of retardation efficacy were observed and recorded.

The percent retardation of offspring in Table LI was

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by visual observation of the hatchling growth of each tree compared to the untreated control plant. A score of 0 percent shows no visible response, a score of 50 percent indicates that the increase in tree growth is only half that of the control plant, or that the tree grew only half as much as the control plant and a rating of 100 percent shows a maximum reaction. This rating system shows any lag in the IT averaging compared to the untreated control plant. The results in Table M represent the average values of 3 replicate measurements.

Table Ll

Effect of Representative Malonic Acid Derivative Compounds on Delaying Plant Growth - Red Maple and Sycamore

Connection ETr. amount per acre) Percentage delay in growth plane (pounds kg / ha Rotaharrn 0 control - 1.12 2.24 0 8 9 Connection 96 1.0 2.0 1.12 2.24 47 42 43 46 Connection 111 1.0 2.0 85 91

The results in Table LI demonstrate that the treatment of red maple and sycamore with certain malonic acid derivative compounds results in a significant retardation of late vigor compared to untreated control red maple and sycamore control.

Claims (4)

claims ^{1 1} "Il ~ 'II ² " ^Y 5 wherein: , Yo * ^ 5 ^»y 6 ¹¹²¹ * ^ Y ^{- Z d} * ^e ^ ^{31 ANSR} P ^ruc b have 1 explained meaning and Y. and Y. are linked together to form a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system which is saturated or unsaturated, wherein the permissible substituents are Z. 4. The method according to claim 1, characterized in that the compound has the following formula: R'-Y ' (Jo in which represent: Z * Q is the same or different and one or more of Is hydrogen or substituted or unsubstituted halogen, haloalkyl, polyhaloalkyl, polyhaloalkoxy, alkyl, alkoxy, alkyl tJiio, alkyl sulfonyl, alkylsulfinyl, aryl, aryloxy, arylthio, arylsulfonyl, ITitro _r cyano, Dialkoxyphosph iη yl, acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino , Sulfonylamino, alkylsulfonylamino, acyloxy, alkenyl or -CH = CHCH = CH-; Y » ₈ is 0, S, HH or IT (alkyl); and R 1 is hydrogen, ammonium, alkylammonium, polyalkylammonium, hydroxyalkylammonium, poly (hydroxyalkyl) ammonium, an alkali metal or alkaline earth metal or substituted or unsubstituted alkyl, hydroxyalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkylaminoalkyl, dialkylaminoalkyl, aryl, mercaptoalkyl, alkylthioalkyl, arylthioalkyl, aryloxyalkyl, alkylsulfonylalkyl, Alkylsulfinylalkyl, acylalkyl, aroylalkyl, dialkoxyphosphinylalkyl, diaryloxyphosphinylalkyl, hydroxyalkylthioalkyl, hydroxyalkylsulfonylalkyl, alkoxyalkylthioalkyl, alkoxyalkylsulfonylalkyl, poly (oxyalkylene) alkyl, cyanoalkyl, hitroalkyl, alkylideneamino »carbamoylalkyl, alkylcarbamoylalkyl, dialkylcarbamoylalkyl, aminoalkyl, acylaminoalkyl, acyloxyalkyl, alkoxycarbonylaminoalkyl, cyanoaminoalkyl, carbamoyloxyalkyl, Alkylcarbamoyloxyalkyl, dialkylcarbamoyloxyalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonylthioalkyl, aminosulfonylalkyl, alkylaminosulfonylalkyl or dialkylaminosulfonylalkyl; wherein the permissible substituents Z are as defined in claim 1 Method according to claim 1, characterized in that the compound has the following formula: Z ^{1 is the} same or different, and is ε п ep з or more of hydrogen or substituted or unsubstituted halo, haloalkyl, polyhaloalkyl, polyhaloalkoxy, alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfonyl, aryl, aryloxy, arylthio, arylsulfonyl, nitro, cyano, Dialkoxyphosphinyl, acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino ,. Sulfonylamino, alkylsulfonylamino, acyl oxy, alkenyl or -GH = CHCH = CH-J Y » ₃₉ is O, S, HH or N (alkyl); and R'o is a derivative salt or derivative salts or Z with that in Ano 1 explained significance · Method according to claim 1, characterized in that the compound has the following formula: 0 0
in which represent: Z _'1O is the same or different and is one or more of hydrogen or substituted or unsubstituted halogen, haloalkyl, polyhaloalkyl, polyhaloalkoxy, alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfinyl, aryl, aryloxy, arylthio, arylsulfonyl, nitro, cyano, Dialkoxyphosphinyl, Acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino, sulfonylamino, alkylsulfonylamino, acyloxy, alkenyl or -CH = CHCH = CH-; Y ' _4O is _O , S, NH or N (alkyl); Y * and Y * j- are independently hydrogen or substituted -134- or unaubstatuiertes halogen, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkylthio, cyano, nitro, Ізосуапо, formyl, amino, hydroxy, alkylcarbonyl, alkylsulfonyl, alkylsulfinyl, malkoxyalkyl, alkylcarbonyl amino, pormylamino, alkylamino, dialkylamino, alkoxycarbonyl, hydroxyalkyl, Polyhaloalkyl or haloalkyl; or У. and Y'j- may be linked together to form a substituted or unsubstituted carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridging ring system which can be saturated or unsaturated зеіп, and R * η is hydrogen, ammonium, alkylammonium, polyalkylammonium, hydroxyalkylammonium, poly (hydroxyalkyl) axmonium, an alkali metal or alkaline earth metal or substituted or unsubstituted alkyl, hydroxyalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkylaminoalkyl, dialkylaminoalkyl, aryl, mercaptoalkyl, alkylthioalkyl, arylthioalkyl, aryloxyalkyl , Alkylsulfonylalkyl, alkylsulfinylalkyl, acylalkyl, aroylalkyl, dialkoxyphosphinylalkyl, diaryloxyphosphinylalkyl, hydroxyalkylthioalkyl, hydroxyalkylsulfonylalkyl, alkoxyalkylthioalkyl, alkoxyalkylsulfonylalkyl, poly (oxyalkylene) alkyl, cyanoalkyl, ectroalkyl, alkylideneamino, carbamoylalkyl, alkylcarbamoylalkyl, dialkylcarbamoylalkyl, aminoalkyl, acylaminoalkyl, acyloxyalkyl, alkoxycarbonylaminoalkyl, cyanoaminoalkyl, carbamoyloxyalkyl , Alkylcarbamoyloxyalkyl, dialkylcarbamoyloxyalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonylthioalkyl, aminosulfonylalkyl, alkylaminosulfonylalkyl or dialkylaminosulfonylalkyl; wherein the permissible substituents Z are as defined in claim 1 meaning. -735 · - Method according to claim 1, characterized in that the compound has the following formula: γ »γ» Q 7 I ⁹ I ⁷ ϊ · -с-с-ϊ _η ¹⁰ \ / ⁸ O in which represent: Z ₁ is the same or different and is one or more of hydrogen or substituted or unsubstituted halo, haloalkyl, polyhaloalkyl, polyhaloalkoxy, alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfinyl, aryl, aryloxy, arylthio, arylsulfonyl, nitro, cyano, dialkoxyphosphinyl , Acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino, sulfonylamino, alkylsulfonylamino, acyloxy, alkenyl or -CH = CHCH = CH-; Y ' ₆ is hydrogen or alkyl; Y'γ, Y'о "Y * о and Y _'1O are independently hydrogen, halogen or alkyl; Y 'is O, S, NH or N (alkyl); and R _'10 is hydrogen, ammonium, alkylammonium, polyalkylammonium, hydroxyalkylammonium, poly (hydroxyalkyl) ammonium, an alkali metal or alkaline earth metal or substituted or unsubstituted alkyl, hydroxyalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkylaminoalkyl, dialkylaminoalkyl, aryl, mercaptoalkyl, alkylthioalkyl, arylthioalkyl, aryloxyalkyl, Alkylsulfonylalkyl, alkylsulfinylalkyl, acylalkyl, aroylalkyl, dialkoxyphosphinyl alkyl, diaryloxyphosphinylalkyl, hydroxyalkylthioalkyl, hydroxyalkylsulfonylalkyl, alkoxyalkylthioalkyl, alkoxyalkylsulfonylalkyl, poly (oxyalkylene) alkyl, cyanoalkyl, nitroalkyl, alkylideneamino, carbamoylalkyl, alkylcarbamoylalkyl, dialkylcarbamoylalkyl, aminoalkyl, acylaminoalkyl, acyloxyalkyl, alkoxycarbonylaminoalkyl, cyanoaminoalkyl, carbamoyloxyalkyl, alkylcarbamoyloxyalkyl, dialkylcarbamoyloxyalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonyl thioalkyl, Arai.no sulfonyl alkyl, Alkylaminoaulf onylalkyl or dialkylaminosulfonylalkyl; wherein the permissible substituents Z are as defined in claim 1 meaning. Method according to claim 1, characterized in that the compound has the following formula: in which represent: Zip is the same or different and is one or more of hydrogen or substituted or unsubstituted halo, haloalkyl, polyhaloalkyl, polyhaloalkoxy, alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfinyl, aryl, aryloxy, arylthio, arylsulfonyl, nitro, cyano, dialkoxyphosphinyl, acyl, Aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino, sulfonylamino, alkylsulfonylamino, acyloxy, alkenyl or -CH = CHCH = CH-; --73 * - ^Υ 'ΐ1' ^Υ * 12 » ^γ * 13 ' ^Υ * 14' ^Υ 'ΐ5" ¹ ^ ^Υ * 16 ^are hydrogen, halogen or alkyl; Y » ₄₂ is 0, S, HH or U (alkyl); and R '.... is hydrogen, ammonium, alkylammonium, polyalkylammonium, hydroxyalkylammonium, poly (hydroxyalkyl) ammonium, an alkali metal or alkaline earth metal or substituted or unsubstituted alkyl, hydroxyalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkylaminoalkyl, dialkylaminoalkyl, aryl, mercaptoalkyl, alkylthioalkyl , Arylthioalkyl, aryloxyalkyl, alkylsulfonylalkyl, alkylsulfinylalkyl, acylalkyl, aroylalkyl, dialkoxyphosphinylalkyl, diaryloxyporphylalkyl, hydroxyalkylthiol, hydroxyalkylsulfonylalkyl, alkoxyalkylthioalkyl, alkoxyalkylsulfonylalkyl, poly (oxyalkylene) alkyl, cyanoalkyl, ITitroalkyl, alkylideneamino, carbamoylalkyl, alkylcarbamoylalkyl , Dialkylcarbamoylalkyl, aminoalkyl, acylaminoalkyl, acyloxyalkyl, alkoxycarbonylaminoalkyl, cyanoaminoalkyl, garbamoyloxyalkyl, alkylcarbamoyloxyalkyl, dialkylcarbamoyloxyalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonylthioalkyl, aminosulfonylalkyl, alkylaminosulfonylalkyl or dialkylaminosulfonylalkyl; wherein the permissible substituents Z are as defined in claim 1 Method according to claim 1, characterized in that the compound has the following formula: γ "
.20 ^Υ 21 Ч J ^Υ 19 f »-C-G-C-N-C ^ ο ο η _τ in which represent: ¹ BR * л-ъ ізѣ the same or different and is one or more of hydrogen or substituted or unsubstituted halogen, haloalkyl, polyhaloalkyl, polyhaloalkoxy, alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfinyl, aryl, aryloxy, arylthio, arylsulfonyl, nitro , Cyano, dialkoxyphosphinyl, acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino, sulfonylamino, alkylsulfonylamino, acyloxy, alkenyl or -CH = CHCH = CH-; Y ^ ₁ - is hydrogen or alkyl} Y ' _1Q , Y'-iQ''^' ^ ^ ^Y> 21 ^are independently hydrogen, halogen or alkyl; Y » ₄₃ is O, S, NH or N (alkyl); and R * ₁₂ i • ³ * ^e ^ ° derivative salt or Z having the meaning explained in claim 1. 10. The method according to claim 1, characterized in that the compound has the following formula: Y 'Y' ^X 24/23 / 22 C 7 * о о in which represent: -133- Z'a ℓ is the same or different and is one or more of hydrogen or substituted or unsubstituted halo, haloalkyl, polyhaloalkyl, polyhaloalkoxy, alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylaulphinyl, aryl, aryloxy, arylthio, arylsulfonyl, Fitro, cyano , Dialkoxyphosphinyl, acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino, sulfonylamino, alkylsulfonylamino, acyloxy, alkenyl or -CH = CHCH = CH-; Y'21 » ^Y * 22 * ^Y> 23» ^Y * 24 » ^Y * 25 ^ ¹ * ^{1 Y>} 26 are ^each independently selected from the group consisting of hydrogen, halogen or alkyl; Y » ₄₄ is 0, S, Ж or N (alkyl); and R '_ is a derivative salt or Z having the meaning explained in claim 1. Method according to claim 1, characterized in that the compound has the following formula: о о in which represent: Zl ₁ - is the same or different and is one or more of hydrogen or substituted or unsubstituted halo, haloalkyl, polyhaloalkyl, polyhaloalkoxy, alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfinyl, aryl, aryloxy, arylthio, arylsulfonyl, nitro, cyano, dialkoxyphosphinyl , Acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino, sulfonylamino, alkylsulfonylamino, acyloxy, alkenyl or -CH = CHCH = CH-; Y » ₂₇ is 0, S, KH or Ii (alkyl); Y * 23 includes _е ^ д substituted or unaubstituiertes, carbozyklisoJies or heterozyklxscb.es ring system, which has been selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or non-aromatic ti see ring system and a Briickenringsystem that may be saturated or unsaturated; r ₄₅ is O, S, NH or Ж (alkyl); and R * 4 is a derivative salt or Z with the meaning explained in claim 1 Method according to claim 1, characterized in that the compound has the following formula: ^R 15 46 wherein represent: Z ' ₁ g is the same or different and is one or more of hydrogen or substituted or unsubstituted halo, haloalkyl, polyhaloalkyl, polyhaloalkoxy, alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfinyl, aryl, aryloxy, arylthio, arylsulfonyl, ureo, cyano, dialkoxyphosphinyl , Acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino, sulfonylamino, alkylsulfonylamino, acyloxy, alkenyl or -CH = CHCH = CH-; Y ' _2g is _O , S, KH or Ii (alkyl); Y * and Y'o-j are independently hydrogen or substituted or unsubstituted halogen, cycloalkyl, isocyano, alkylsulfonyl, Alkylsulfinyl, alkylamino, dialkylamino, alkoxycarbonyl, alkenyl, alkynyl, alkyl, alkoxy, alkylthio, cyano, ureo, formyl, amino, hydroxy, alkylcarbonyl, dialkoxyalkyl, alkylcarbonylamino, formylamino, hydroxyalkyl, polyhaloalkyl or haloalkyl; or Y * ^ ₀ and Y ^ ₁ may be linked together to form a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridging ring system which may be saturated or unsaturated; Y _'46 is O, S, HH or Ii (alkyl); and R'-c is a derivative or Z having the meaning explained in claim 1. 13. The method according to claim 1, characterized in that the compound has the formula: γ »γ» \ ^{4 33} 0 0 in which represent: ZIr is the same or different and is one or more of hydrogen or substituted or unsubstituted halo, haloalkyl, polyhaloalkyl, polyhaloalkoxy, alkyl, acyloxy, alkylthio, alkylsulfonyl, alkylsulfinyl, aryl, aryloxy -ІН-Z- Arylthio arylsulfonyl, hitro, cyano, dialkoxyphosphinyl, acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino, sulfonylamino, alkylsulfonylamino, acyloxy, alkenyl or -CH = CHCH = CH-; Y ^ ₂ is 0, S, H or Ж (alkyl); Yi and Yi. are independently hydrogen or substituted or unsubstituted halo, alkyl, alkoxy, alkylthio, polyhaloalkyl or haloalkyl; or Y '03 and Y' 04 may be linked together to a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system and a bridging ring system, which may be saturated or unsaturated; Y _'47 is O, S, PN or Ή (alkyl) and R ' * c is a derivative salt or Z having the meaning explained in claim 1. A method according to claim 1, characterized in that the compound has the following formula: γ »γ». in which represent: R * -γ is a substituted or unsubstituted heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, or a polycyclic aromatic or nonaromatic ring system and a bridging ring system which may be saturated or unsaturated; Y is ₃₅ , 0, S, N or U (alkyl); Y * _g and Y'37 are independently hydrogen or substituted or unsubstituted halo, cycloalkyl, isocyano, alkylsulfonyl, alkylsulfinyl, alkylamino, dialkylamino, alkoxycarbonyl, alkenyl, alkynyl, alkyl, alkoxy, alkylthio, cyano, nitro, pormyl, amino, hydroxy Alkylcarbonyl, dialkoxyalkyl, alkylcarbonylamino, formylamino, hydroxyalkyl, polyhaloalkyl or haloalkyl; or Y ', g and Y' yj may be linked together to form a ε-substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system and a bridging ring system which may be saturated or unsaturated; Y _'48 is O , S, N or Έ (alkyl); and R * о is a derivative salt or Z having the meaning explained in claim 1. 15 · Procedure after. Claim 1, characterized in that the compound has the following formula: T7 но-с-с-с-ни Il Il
о о 16. »Process according to claim 1, characterized in that the compound has the following formula: HO-C-C-C-HH- ^ II ⁰ ° Cl 17. The method according to claim 1, characterized in that the compound has the formula: II II GH ₃ CH ₂ -OG-CH ₂ -C -HN 3r 18. The method according to claim 1, characterized in that the compound has the following formula: HO-C-CH ₂ -C-NH br CH- 19 · Method according to claim. 1, characterized in that the compound has the following formula: но-с-с-с H Il о о br 20. The method according to claim 1, characterized in that the compound has the following formula: но с-с-с-
о о Cl 21. The method according to claim 1, characterized in that the compound has the following formula: V7 HO-С-С-С-ИИ- Il о о Cl 22. The method according to claim 1, characterized in that the compound has the following formula: V7 ³² Il l | Method according to claim 1, characterized in that the compound has the following formula: HO-C-C-C-0 0 Cl Method according to claim 1, characterized in that the compound has the following formula: GH ₃ CH ₂ - • o-σ-σ-с-ш Il Il о о br Method according to claim 1, characterized in that the compound has the following formula: V7 но-с-- с-с-ни- 0 o 26. The method according to claim 1, characterized in that the compound has the following formula: Process according to claim 1, characterized in that the compound has the formula: 3erlin _# the 22. 8. 88 68 563 18 A method of retarding plant growth characterized by applying to the plant an effective amount of a compound of the following formula sufficient to retard plant growth: ^{11 I-1} I- jj ° § - ^Y 2 - "2 ^Y 5 4 in which: R ₁ and R ₂ are independently a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridging ring system which may be saturated or unsaturated wherein the permissible substituents (Z) are the same or different and are one or more of hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, pormyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, Formamidine®, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, azido, azo, aminocarbonyl, alkylaminocarbonyl, hydrazono, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminoth iocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, pormamido, alkyl, alkoxy, polyhaloalkyl, polyhalogenoalkoxy, alkoxycarbonyl, substituted amines in which the permissible substituents are identical or different and -ΊλΖ- the following are: one or two propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; Alkylthio, polyhalogenoalkylthio, alkylsulfinyl, Polyhalogenalkylsulfinyl, alkylsulfonyl, PolyhAlogenalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, Polyhalogenalkylsulfonylamino, Polyhalogenalkylcarbonylamino, trialkylsilyl, Aryldialkylailyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, Polyhalogenalkenyl, alkenyloxy, alkynyl, alkynyloxy, Polyhalogenoalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, Alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfone yl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyl oxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenyl-3-sulfonyl, isocyano, aryloxysulfonyl, preplyloxy, areyl, haloacyl, polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, Polyhalogenacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamines, aryl (alkyl) amino, aralkylamines, alkoxyalkylphosphinyl, alkoxyalkylphosphine thioyl , Alkylhydroxyphosphinyl, dialkoxyphosphino, -7 * 3- Hydroxyamines, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, diazo, alkylidene, alkylimino, hydrazones, semicarbazones, dialkylsulfonium, dialkylsulfuranylidene, dialkyloxosulfuranylidene -Χ, β X, -X ss R- ,, = s X-R-, I * \ f I! -X - R-, -P- YoR _A »-Ym ~ V ^ I-10 ν Y ₉ R ₅ Y ₉ R ₅ or , ^Y 8 ^R 4 ; or R ₁ and Rp are independently hydrogen or derivative salts or a substituted heteroatom or a substituted carbon atom or a substituted or unsubstituted, branched or straight chain having two or more carbon atoms or heteroatoms in any combination, the permissible substituents being Z; Y ₁ and ΥΥ are independently a substituted or unsubstituted heteroatom, the permissible substituents being Z; Y, and Y are independently hydrogen or a substituted or unsubstituted heteroatom or a substituted carbon atom or a substituted or unsubstituted, branched or straight chain having two or more carbon atoms or heteroatoms in any combination, or halo, alkylcarbonyl, pormyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, Alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, trialkylsilyloxy, aryldialkylsilyloxy, triaryl silyloxy, formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, imino, hydrazones, azo, aminocarbonyl, alkylaminocarbonyl, azido, dialkylaminooarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitre, oyano, hydroxycarbylbindyl derivative salts, formamides, alkyl, alkoxy, polyhaloalkyl Polyhaloalkoxy, alkoxycarbonyl, subsituted amino wherein the permissible substituents are the same or different and represent one or two of propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; Alkylthio, polyhalogenoalkylthio, alkylsulfinyl, Polyhalogenalkylsulf ynyl, alkylsulfonyl, polyhaloalkyl sulfonyl, alkylsulfonylamino, alkylcarbonylamino, Polyhalogenalkylsulfonylamino, Polyhalogenalkylcarbonylamiло, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, Polyhalogenalkenyl, alkenyloxy, alkynyl, Alkynyloxy, polyhalogenoalkenyl oxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanes}, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl , Haloalkenyl ». Haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, Halogenalkynyloxy, Halogenalkynylthio, haloalkenylsulfonyl, Polyhalogenalkenylsulfonyl, isocyano, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, PoIyhalogenacyl, aryloxycarbonyl, Amiлоsulfonyl, Alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxysralkoxy, carboxy- alkylthio, alkoxycarbonylalkoxy, acyloxy, Halogenacyloxy, PoIyhalogenacyloxy, aroyloxy, alkylsulfonyloxy, Alkenylsulfonyloxy, arylsulfonyloxy, Halоgenalkylsulfonyloxy, polyhaloalkyl 3ulfonyloxy, aroylamino, Halogenecylamino, alkoxycarbonyloxy, Aryl3Ulfonylaminо, aminocarbonyloxy, cyanato, isocyanates isothiocyano, Gycloalkylamino, trialkylammonium, arylamino, aryl (alkyl) amino, aralkylamino, Alkoxyalkylpho3phinyl, Alkoxyalkylpho sphino thioyl, Alkylhydroxypho sphinyl, Dialkoxypho sphino, hydroxyamino, alkoxyamino, aryloxyatnino, TTD
-A, -A - Л-, IT ⁷ H ⁷ -X - R ₃ , - PY ₈ R ₄ , -Y ₁₀ - PY ₈ R ₄ ^Y 9 ^R 5 ^Y 9 ^R 5 ^Y S ^R 4 Ϊ9Η5
wherein the permissible substituents are Z; Υ "and Y _{4 taken} together are oxo, thiono, diazo, = X or = XR-, or substituted or unsubstituted alkylidene, alkylimino, hydrazones, dialkylsulphanylidene, dialkyloxoaulfuranylidene, semicarbazono, hydroxylprepo, alkoxyimino or aryloxyimino, where the permissible substituents are Z; Y.sup.- and Y.sup.- may be linked together to form a 3-membered or unsubstituted, saccharocyclic or heterocyclic ring system selected from a monocyclic group. aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system and a bridging ring system which may be saturated or unsaturated, the permissible substituents being Z; Ya and Yg are independently oxygen or sulfur; where: X is a covalent single or double bond, a substituted or unsubstituted heteroatom or substituted carbon atom, or a substituted or unsubstituted, branched or straight chain having two or more carbon atoms or heteroatoms in any combination, the permissible substituents being Z; R ₃ is a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridging ring system in which it may be saturated or unsaturated the permissible substituents Z are; R_ is a substituted heteroatom or substituted carbon atom or a substituted or unsubstituted, branched or straight chain having two or more carbon atoms or heteroatoms in any combination where the permissible substituents are Z; Yj and Y ₁₀ are independently oxygen or sulfur; Yg and Yq are independently oxygen, sulfur, amino or a single covalent bond, and R, and Re are independently hydrogen or substituted or unsubstituted alkyl, alkenyl, alkynyl, polyhaloalkyl, phenyl or benzyl, the permissible substituents being Z. 2. The method according to claim 1, characterized in that the compound has the formula: Y Y H ₁ -Y ₁ - о о Jj-I ₂ -B ₂ in the following represent: R and Rp are independently a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or non-aromatic ring system, and a bridged ring system that is saturated or unsaturated may be unsaturated, wherein the permissible substituents Z are as defined in claim 1 meaning; or or ^Y 9 ^E 5 R and R ₂ are independently hydrogen or derivative salts, or a substituted heteroatom or substituted carbon atom or a substituted or unsubstituted, branched or straight chain having two or more carbon atoms or heteroatoms in any combination, the permissible substituents being Z; Y and Y ₂ are independently a substituted or unsubstituted heteroatom, the permissible substituents being Z; Y and Y are independently hydrogen or a substituted or unsubstituted heteroatom or a substituted carbon atom or a substituted or unsubstituted, branched or straight chain having two or more carbon atoms or heteroatoms in any combination or halogen, alkylcarbonyl, pormyl, alkylcarbonylalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio , Polyhaloalkenylthio ,. Thiocyano, propargylthio, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, iormamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, am, no, hydrazino, azo, aminocarbonyl, alkylaminocarbonyl, azido, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, Hydroxycarbonyl and derivative заіге, pormamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino wherein the permissible substituents are the same or different and one or two of propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; Alkylthio, polyhalogenoalkylthio, alkylsulfinyl, Polyhalogenalkylsulfinyl, alkylsulfonyl, Polyhalogenalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, Polyhalogenalkylsulfonylamino, Polyhalogenalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, Polyhalogenalkenyl, alkenyloxy, alkynyl, alkynyloxy, Polyhalogenoalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicarbazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyirninomethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted aryl -7 * 3- hydrazonomethyl, a hydroxy group condensed with a mono-, di- or polysaccharide, haloalkyl, haloalkenyl, haloalkynyl, alkoxyalkyl, aryloxy, aralkoxy, arylthio, aralkylthio, alkylthioalkyl, arylthioalkyl, arylsulfinyl, aryl-axilfonyl, haloalkylsulfinyl, halo-alkylsulfonyl , Haloalkenyloxy, haloalkynyl oxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, isocyano, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, polyhaloacyl, aryloxycarbonyl, ami, sulfonyl, alkylamino sulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, Polyhalogenacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl- (alkyl) a mi ri о, Агаікуіятпіло, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyakino, alkoxyamino, aryl охуатп 1 no, -X, -X = R, 3 Y ₇ Y ₇ И ⁷ II ⁷ -X - R 1, - P- Y ₈ R ₄ , -Y ₁₀ - P- Y ₈ R ₄ ^Y 8 ^R 4 wherein the permissible substituents are Z; or Y and Y together are oxo, thiono, diazo, = X or = X-R_, or substituted or unsubstituted alkylidene, -730- Alkylimino, hydrazono, dialkylsulfurylanylidene, dialkyloxosulfuranylidene, semicarbozono, hydroxyamines, alkoxyimines or aryloxyimino, wherein the permissible substituents are Z; Y, - and Yg are independently oxygen or sulfur; where represent X is a covalent single or double bond, a substituted or unsubstituted heteroatom or substituted carbon atom, or a substituted or unsubstituted, branched or straight chain having two or more carbon atoms or heteroatoms in any combination wherein the permissible substituents are Z; R 1 is a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridging ring system which may be saturated or unsaturated, wherein the permissible Substituents Z are; R- is a substituted heteroatom or substituted carbon atom or a substituted or unsubstituted, branched or straight chain having two or more carbon atoms or heteroatoms in any combination, the permissible substituents being Z; Yj and Y ₁₀ are independently oxygen or sulfur; Yg and Yq are independently oxygen, sulfur, amino or a covalent single bond; and R. and Rg are independently hydrogen or substituted or unsubstituted alkyl, alkenyl, alkynyl, polyhaloalkyl, phenyl or benzyl, the permissible substituents being Z · • 3 * - Ii и O Cl Composition for delaying plant growth, characterized in that it contains an acceptable carrier medium and an effective amount of a compound of the following formula, which is sufficient to increase the rate of plant growth; Y Y ^Y 3 4 R ₁ -Y ₁ -C С С - Y ₂ - R ₂ ^Y 5 ^Y 6 in which represent: R ₁ and R ₁ are independently a substituted or unsubstituted carbocyclic ring system selected from a monocyclic aromatic or nonaromatic ring system, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridging ring system which may be saturated or unsaturated R ₁ and Rp are independently hydrogen or derivative salts or a substituted heteroatom or substituted carbon atom, or a substituted or unsubstituted, branched or straight chain having z'.vci or more carbon atoms or heteroatoms in any combination; Y ₁ and Yp are independently a substituted or unsubstituted heteroatom; Y, and Y. are linked together to a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaronative ring system, a bicyclic aromatic or heterocyclic ring system -151- non-aromatic ring system, a polycyclic aromatic or non-aromatic ring system, and a β-ring system which may be saturated or unsaturated; Y ₅ and Yg are independently oxygen or sulfur, the permissible substituents Z being as defined in claim 1. 43. A composition according to claim 42, characterized in that a compound is selected one of the following formula: 26 γ γ 25 ^γ 24 X-C - Y 22 - ^C - 5 - ^Y 21 \ _ in which represent: Z. is independently substituted or unsubstituted halogen, haloalkyl, polyhaloalkyl, polyhaloalkoxy. Alkyl, alkoxy, alkylthio, alkylsulfonal, alkylsulfinyl. Aryl, aryloxy, arylthio, arylsulfonyl, nitro, cyano, dialkoxyphosphinyl, acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino, sulfonylamino, alkylsulfonylamino, acyloxy, alkenyl or -CH = CHCH = CH-; η i3t is a value between 0 and 5; Y ₂₁ is O, S or ITR-j, wherein R _{1 is} hydrogen or alkyl; Y ₂₂ is O, S, Ж or W (alkyl); Υ ₂ _, Υ _2Λ , Y ₂ , - and Y ₂ g are independently hydrogen, alkyl or halogen; and R ₁₂ is hydrogen, ammonium, alkylammonium, polyalkylammonium, hydroxyalkyl ammonium, poly (hydroxyalkyl) ammonium, an alkali metal or alkaline earth metal or substituted or unsubstituted alkyl, hydroxyalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkylaminoalkyl, dialkylaminoalkyl, aryl, mercaptoalkyl, alkylthio al kyl, aryl ithyl, aryl oxyalkyl, alkylsulfonylalkyl, alkylsulfinylalkyl, "acylalkyl, aroylalkyl, dialkoxyphosphinylalkyl, diaryloxyphosphinylalkyl, hydroxyalkylthioalkyl, hydroxyalkylsulfonylalkyl, alkoxyalkylthioalkyl, alkoxyalkylsulfonylalkyl, polo (oxyalkylene) alkyl, cyanoalkyl, nitroalkyl, alkylideneamino, carbamoylalkyl , Alkylcarbamoylalkyl, dialkylcarbamoylalkyl, aminoalkyl, acylaminoalkyl, acyloxyalkyl, alkoxycarbonylaminoalkyl, cyanoaminoalkyl, carbamoyloxyalkyl, alkylcarbamoyloxyalkyl, dialkylcarbamoyloxyalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonylthioalkyl, aminosulfonylalkyl, alkylaminosulfonylalkyl or dialkylaminosulfonylalkyl; hey ₅ R ₈ -Y ^ -CCQY -C-C-C- ¹⁴ ! ^s in which represent: Z ₂ is independently substituted or unsubstituted halo, haloalkyl, polyhaloalkyl, polyhaloalkoxy, alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfinyl, aryl, aryloxy, arylthio, Arylsulfonyl, nitro, cyano, cialkoxyphosphinyl, acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino, sulfonylamino, alkylsulfonylamino, acyloxy, alkenyl or -CH = CHCH = CH-; η is a '.Vert between 0 and 5; Y ₃ is O, S odor NRg, wherein Rg is hydrogen or alkyl; Y ₁₄ is O ₁ S, NH or N (alkyl); Y ₁₅ and Y ₁₆ have the meaning explained in claim 37; or Y ₁ C and Y ^ g may be linked together to a substituted or unsubstituted heterocyclic ring system selected from a monocyclic aromatic or non-aromatic Rinrsystom, a bicyclic aromatic or non-aromatic ring system, a polycyclic aromatic or non-aromatic ring system and a bridging ring system which is saturated or may be unsaturated; and R ₃ is hydrogen, ammonium, alkylammonium, polyalkylammonium, hydroxyalkylammonium, poly (hydroxyalkyl) ammonium, an alkali or alkaline earth metal or substituted or unsubstituted alkyl, hydroxyalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkylaminoalkyl, dialkylaminoalkyl, aryl, mercaptoalkyl, alkylthioalkyl, arylthioalkyl, aryloxyalkyl , Alkylsulfonylalkyl, alkylsulfinylalkyl, acylalkyl, aroylalkyl, dialkoxyphosphinylalkyl, Diaryloxyphosphinylalkyl, hydroxyalkylthioalkyl, hydroxyalkylsulfonylalkyl, alkoxyalkylthioalkyl, alkoxyalkylsulfonylalkyl, poly (oxyalkylene) alkyl, cyanoalkyl, ilitroalkyl, alkylideneamino, carbamoylalkyl, alkylcarbamoylalkyl, dialkylcarbamoylalkyl, aminoalkyl, acylatinoalkyl, acyloxyalkyl, alkoxycarbonylaminoalkyl, cyanoaminoalkyl, carbamoyloxyalkyl, Alkylcarbanoyloxyalkyl, dialkylcarbanoyloxyalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonylthioalkyl, aminosulfonylalkyl, alkylaminosulfonylalkyl or dialkylaminosulfonylalkyl; / ³⁰ σ с ^R 14 "" ^Y 28 "" ^C in which represent: Zc is independently substituted or unsubstituted halo, haloalkyl, polyhaloalkyl, polyhaloalkoxy, alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfinyl, aryl, aryloxy, arylthio, arylsulfonyl, mtro, cyano, dialkoxyphosphino, acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino, sulfonylamino, Alkylsulfonylamino, acyloxy, alkenyl or -CH = CHCH = CH-; η is a 7 / ert between 0 and 5; Y ₂₇ is O, S or ITR ₁ -> wherein R ₁ , - is hydrogen or alkyl 13t; Y ₂₈ is O, S, Ш or IT (alkyl); Y ₂ Q, Y ₂ O 3, ¥ 33 ^and ^ 34 ^are independently hydrogen, alkyl or halogen; and R ₁ . is the same vn.e R ₁₂ ; ^R 16 - ^Y 36 - ^{C C} - ^C - ^Y 35 A ^ in which represent: Zp * is independently substituted or unsubstituted haloalkyl, polyhaloalkyl, polyhaloalkoxy, alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfinyl, aryl, aryloxy, arylthio, arylsulfonyl, nitro, cyano, dialkoxyphosphinyl, acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino, sulfonylarnino, Alkylsulfonylamino, acyloxy, alkenyl or -CH = CHCH = CH-; η is a './ert zv / ischsn 0 and 5; Y ₃₅ is O, S or NR ₁₇ , wherein R ₁₇ 'is hydrogen or alkyl; Y - ,,. is O or S; and R ^ g is the same as ^ ₁₂ * wherein the permissible substituents for the above formulas Z are as defined in claim 37. 14. A composition according to claim 42, characterized by a content of a compound of the following formula: -tr? - Y Y 25 24 26 23 С - C ^ / _Z ч ^R 12 " ^Y 22"? "°" Г. "'21 О О in which: Z. is independently substituted or unsubstituted
Haloalkyl, polyhaloalkyl, polyhaloalkoxy, alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfinyl, aryl,
Aryloxy, arylthio, arylsulfonyl, nitro, cyano, dialkoxyph & sphinyl. Acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino, sulfonylamino, alkylsulfonylamino,
Acyloxy, alkenyl or -CH = CHCH = CH-; η is a Jert between O and 5; Y ₂₁ is C, S or HR., Wherein, I is ₁ -hydrogen or Al1; Y ₂₂ is O, S, MH or il (alkyl); ^Y 23 ' ^Y 24' ^Y 25 ^{and Y} 26 ^are independent of each other; vassar, alkyl or halogen; and R ₁₂ has the meaning explained in claim 3G; wherein the permissible Suostituenten Z are as explained in claim 33 meaning. 45. A composition according to claim 42, characterized by a content of a compound of the following formula: ^Y 32. Y ₃₁ ^Y 33 / \ / 30 ^Y 34 \ / ^Y 2-9 ^l4 14 '28 " in which: Zj- is independently substituted or unsubstituted halo, haloalkyl, polyhaloalkyl, polyhaloalkoxy. Alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfinyl, aryl, aryloxy, arylthio, arylsulfonyl, uitro, cyano, dialkoxyphosphinyl, acyl aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino, sulfonylanino, alkylsulfonylarnino, acyloxy, alkenyl or -CH = CHCH = CH-; η is a './location between 0 and 5; Y ₂₇ is 0, S or i ^ ₁₅ »where .I _{15 is} hydrogen or alkyl is; Y ₂₈ is C ₁ S,; JH or N (alkyl); ^Y 29 ' ^Y 30' ^Y 31 ' ^Y 32' ^Y 33 and ^C ' ^Y "4 ^sinc ^ independently, or alkyl, alkyl or halogen; R has the meaning explained in claim 37; wherein the permissible substituents Z are as defined in claim 37. 46. A composition according to claim 42, characterized by a content of a compound of the following formula: ^R i6 - ^Y 36 - ^c represent woriii following: Z is independently substituted or unsubstituted halo, haloalkyl, polyhaloalkyl, polyhaloalkoxy, alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfinyl, aryl, aryloxy, arylthio, arylsulfonyl, nitro, cyano, dialkoxyphosphinyl, acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino, sulfonylamino Alkylsulfonylamino, acyloxy, alkenyl, or -CH = CIiCH = CH-; η is sin value between о and 5; Y ₃₅ is 0, 3 or I ¹ ^ ₁₇ . wherein, ^ _{17 is} hydrogen or alkyl; Y ₃₆ is 0 or S; and ^In this ^regard , the meaning of the claimed substituents Z has the meaning ^{given in} Ars ^p 39. 47. The composition of claim 42, characterized by a content of a compound of the following formula: YY ^T 16 T15 -Y. .-C-C-C-Y in which: Z "is independently substituted or unsubstituted halogen, haloalkyl, polyhaloalkyl, polyhaloalkoxy. Alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfinyl, aryl, aryloxy, arylthio, arylsulfonyl, nitro, cyano, dialkoxyphosphinyl, acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino, sulfonylanino, alkylsulfonylamino, acyloxy, alkenyl or -CH = CHCH = CH-; η is a fourth between O and 5; Y ₁₃ is O , S or KRg, wherein R _{c is} hydrogen or alkyl; Y ₁₄ is O, S, UH or N (alkyl); Y ₁₅ and Y ₁₆ are independently hydrogen, alkyl, halogen, alkoxy, alkylthio, alkenyl, alkylnyl, hydroxy, cyano, nitro, formyl, amino, alkylcarboriyl, oialkoxyalkyl, alkylcarbonylamino, formylamino, hydroxyalkyl, haloalkyl or polyhaloalkyl, among the following Requirements; (a) when Y _{15 is} alkoxy other than ilcthoxy, at least one of Y ₁₆ and Z _{2 is} other than hydrogen; (b) when Y _{15 is} acyl, cyano or nitro, then Y is ₁₆ Alkyl, alkenyl, alkynyl or halogen; (c) when Y _{15 is} hydroxy or ilercapto then Z_ is other than hydrogen; (d) if Y _{15 is} amino or quialkylanino and Y _{16 is} hydrogen, then \
4-Iodobenzoyl; 7 , then neither is 2,6-dimethyl or ortho-2-fluoro (e) when Y ^ _{5 is} alkylamino and Y _{16 is} methyl then Zp is other than hydrogen; (f) when Y _{15 is} bromine and Y _{16 is} hydrogen, then Z p is other than hydrogen or 2, o -diaethyl and further provided that at least one of Y ₁₅ and Y _{16 is} other than hydrogen; Y ₅ and Y, - are independently oxygen or sulfur; where the permissible substituents Z are as explained in A. award 1 meaning. 43. A composition according to claim 47, characterized by a content of a compound of the following formula: 8 14 "" 13Лг- O О (Z ₂ ) wherein Nitrogen, Oxygen, Hydrogen, 3 2 C-C-C Зг 28. The method according to claim 1, characterized in that the compound has the following formula: CH ₃ CH ₂ - О - С - CH ₂ - С - NH Зг 29. A method according to claim 1, characterized in that the compound is applied to the plant in an amount sufficient to retard plant growth without causing substantial phytotoxicity. 30. The method according to claim 1, characterized in that the Vorbindung applied to the plant at a time before the reproductive Jachstumsphasc the plant ivi rd. A method according to claim 1, characterized in that the compound is applied to the plant at a time during the reproductive phase of the plant. A method according to claim 1, characterized in that the compound is applied to the plant at a concentration of between about 0.001 and about 100 pounds of the compound per acre. 33. The method according to claim 1, characterized in that the compound is in a concentration between about O ₁ ol and about 15 pounds of compound per acre 0.0112 and 16.8 kg / ha is applied to the plant. 34. The method according to claim 1, characterized in that it is the plant is a plant for agriculture or horticulture, wood plants, ornamental plants or grasses. 35. The method of claim 1, characterized in that the plant includes a red maple _; Sycamore, Red Oak, American Elm, Linden, Gingko, Oak, Ash, Maple, Apple Trees, Chinese Elm, Crab Apple, Russian Olive, Silver Maple, Sugar Maple, Vine-rich, Poplars and Conifers are selected wood plant. 36. The method according to claim 1, characterized in that the plant is selected from corn, cotton, sweet potatoes, '.Veißkartoffein, alfalfa, wheat, log, rice, barley, oats, millet, dried beans, soybeans, sugar beets, sunflowers, tobacco , Tomatoes, canola, deciduous fruits, citrus fruits, tea, coffee, olives, pineapples, Запапеп, sugarcane, cocoa, oil palms, herbaceous outdoor plants, woody shrubs, grasses, ornamental plants, evergreen plants, trees and flowers. A method according to claim 1, characterized in that the compound is used in combination with one or more other biologically active compound (s). 38. The method according to claim 1, characterized in that it is the compound is a derivative salt. 39. The method according to claim 38, characterized by
in that the derivative salt is chosen from an alkali metal, an alkaline earth metal, ammonium, alkylammonium, polyalkylammonium, hydroxyalkylammonium, poly (hydroxyalkyl) ammonium or mixtures thereof. 40. The method according to claim 1, characterized in that the compound has the following formol: HO - C - C - C - NH - (/ y - CF ₃
OO 41. The method according to claim 1, characterized in that the compound has the following formula: CH ₃ OH Cl CH 1 -C 3 -C-C-C-NH A method according to claim 1, characterized in that the compound has the formula: ό ύ π π г * V ^ _{4 15} Methoxy, R _{8 is} C ₁ -C ₈ alkyl and Zg, Cl, Br, F or CP.