DD257572A5 - PROCESS FOR INCREASING THE REFUND - Google Patents

Abstract

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

Description

The invention relates to a process for increasing crop yield using malonic acid derivative compounds. The invention further relates to compositions containing malonic acid derivative compounds. The inventive method is used in horticulture and agriculture.

Characteristic of the known state of the art

Certain malonic acid derivative compounds have been known for some time in the art. See, for example, U.S. Patent Nos. 2,504,986 and 3,254,108. Some malonic acid derivative compounds have been described in the art as capable of inducing certain plant growth-regulating reactions such as preventing fruit shedding, rooting of cuttings, and production of parthenogenetic fruits.

No. 3 072 473 discloses N-arylmalonamide acids and their esters and salts, Ν, Ν'-diarylmalonamides, N-alkyl-N-arylmalonamide acids and their esters and salts, and N, N'-dialkyl-Ν, Ν ' diarylmalonamides which may be useful as plant growth regulators and herbicides. The DA-PS 84 39 803 (1984) describes Malonsäureanilidderivatverbindungen, which may be useful as plant growth regulators. The plant growth-regulating properties of substituted malonyl monoanilides are described by Shindo, N. and Kato, M. _# Meiji Daigaku Noogaku-bu Kenkyu Hokoku, Vol. 63, pp. 41-58 (1984).

However, certain malonic acid derivative compounds and the use of malonic acid derivative compounds to enhance yields, as described below, have not been published in the art.

Aim of the invention

The aim of the invention is the provision of new methods for increasing the crop yield.

Explanation of the essence of the invention

The invention has for its object to find * new compounds that cause an increase in crop yield.

According to the invention, a method for increasing crop yield is provided by using malonic acid derivative compounds.

According to the invention, novel malonic acid derivative compounds and processes for their preparation are also provided. These and other objects will become apparent to those skilled in the art from the discussion herein. ,

In the method according to the invention for increasing the yield, an effective amount of a compound according to formula which is sufficient to increase the yield is used

Y Y 3/4

C CY _9- R ..

U * ⁴

^y 5 ^Y 6

wherein R ₁ , R ₂ , Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ and Y _{& have} the meanings later defined th * applied to the plant.

As pointed out above, the invention relates to a process for increasing the yield through the use of certain malonic acid derivative compounds. In particular, the invention includes a method for increasing the yield, which comprises applying to the plant an effective amount of a compound of the following formula sufficient to increase the yield;

Y Y

^T 3 ^T

^R 1 - ^Y 1 - ^{C C C} - ^Y 2 - ^R 2

Jl M

Y Y

5 ^T 6

wherein represent:

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

-77- 39/3 / *

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, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, azido, Azo, aminocarbonyl, alkylarainocarbonyl, hydrazino, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamides alkyl, alkoxy, polyhalo ..genalkyl, 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, polyhalogenoalkylthio, alkylsulfinyl, Polyhalogenalkylsulfinyl, alkylsulfonyl, Polyhalogenalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, Polyhalogenalkylsulfonylaraino, 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, 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, Polyhalogenacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, Arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonyloxy, acyloxy, haloacyloxy, polyhalogenacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino. no, trialkylammonium, arylamino, aryl (alkyl) amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyaminoj alkoxyamino, aryloxyamino, aryloxyimino, ox o, thiono, diazo, alkylidene, alkyliraino, hydrazono, semicarbazones, dialkylsulphonium, dialkylsulphanylidene, dialkyloxosulphanylidene, "" X, - X, X = "z * ⁼ X""·" · »» "

Y ₇ Y ₇

I! II

.χ - R ₃ ,. , ρ _{ΥΛ f} -Y ₁₀ - P - Y ₈ R ₄

Y ₉ R ₅ Y ₉ R ₅

^Y 8 ^R 4

; or

Y ₉ R 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 containing two or more carbon

Matter atoms or heteroatoms in any combination, wherein the permissible substituents Z are as defined above;

Y and Y- are independently a substituted or unsubstituted heteroatom, the permissible substituents being Z as defined above;

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, alkoxycarbonylalkylthio, Polyhalogenalkenylthio, thiocyano, propargylthio, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino ', Alkylsulfamido, Dialkylsulfamido, alkoxysulfonyl, Polyhalogenalkoxysulfonyl, hydroxy, amino, hydrazino, azo, aminocarbonyl, alkylaminocarbonyl, azido, dialkylaminocarbonyl, aminothiocarbonyl, Älkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano , Hydroxycarbonyl and derivative salts, formamides alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino wherein the permissible substituents are the same or different and represent the following one or two of propargyl, alkoxyalkyl, alkylthioalkyl. Alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; Alkylthio, polyhalogenoalkylthio, alkylsulfinyl, Polyhalogenalkylsulfinyl, alkylsulfonyl, Polyhalogenalkylsulfonyl, alkylsulfonylamino, alkylcarbonylamino, Polyhalogenalkylsulfonylamino, Polyhalogenalkylcarbonylamino, trialkylsilyl, triarylsilyl, aryldialkylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, Polyhalogenalkenyl, alkenyloxy, alkynyl, alkynyloxy, Polyhalogenoalkenyloxy, polyhaloalkynyl, polyhaloalkynyloxy, polyfluoroalkanol, cyanoalkylamino, semicar

"JS-

bazonomethyl, alkoxycarbonylhydrazonomethyl, alkoxyiminoraethyl, unsubstituted or substituted aryloxyiminomethyl, hydrazonomethyl, unsubstituted or substituted arylhydrazone-niethyl, 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, Polyhalogenacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, Acyloxy, haloacyloxy, polyhalogenacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, halo genacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl (alkyl) amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino,

-X, -X ss R. ,,

Y Y

Il

-X - R ₃ , - P- Y ₈ R ₄ . -Y ₁₀ - P- Y ₈ R ₄

YgR ₅ "Y ₉ R ₅

or

Y ₉ R ₅

wherein the permissible substituents Z are as defined above; or

Υ- and Y _{4 taken} together are oxo, thiono, diazo, = X or = X-R_, or substituted or unsubstituted alkylidene, alkylimino, hydrazono, dialkylsulfonium, dialkyloxosulfuranylidene. Semicarbazones, hydroxyimino, alkoxyimino, or aryloxyimino, wherein the permissible substituents Z are as hereinbefore defined;

Y_ and Y ₄ may be joined together to-one substituted or unsubstituted, carbocyclic or heterocyclic Ringsystera that has been selected is saturated under 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, or 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, 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 non-aromatic ring system and a bridge ring system which may be saturated or unsaturated, wherein the permissible substituents Z are as defined above;

R _x 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 Z are as hereinbefore defined;

Y ₇ and Y ₁₀ are independently oxygen or sulfur;

Yg and Yq are independently oxygen, sulfur, amino or a covalent single bond; and

R. and R ₅ are independently hydrogen or substituted or unsubstituted alkyl, alkenyl, alkynyl, polyhaloalkyl. Phenyl or benzyl, where the permissible substituents Z are as defined in the preceding ^ meaning.

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 considered favorable that all of the compounds of formula 1 are compounds which have no unfilled binding positions. With respect to the malonic acid derivative compounds of this invention, it is best that when both Y and Y are -NH-, R and R_ are independently components other than hydrogen, alkyl or aryl.

Hydrogen or derivative salts according to the invention refer to hydrogen or any suitable derivative salt substituents, which may therefore be substituted. To explain

___ 257 57 *

Derivative salt substituents are, for example, ammonium, alkylammonium, polyalkylammonium, hydroxyalkylammonium, poly (hydroxyalkyl) aramonium, alkali metals, alkaline earth metals and the like, including mixtures thereof.

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

^B l Z '

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 having 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 and Y ₄ linked together in Formula 1 may be any of the monocyclic ring systems of R ₁ , R ₂ and R ₃ correspondingly positioned in Formula I ₁ .

Ring-forming heteroatoms may in some cases carry oxygen atoms, e.g. 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 ₁

which contain at least 3 ring-forming atoms can attach carbonyl, thiocarbonyl, substituted or unsubstituted imino or substituted or unsubstituted methylidene groups. The group designated Z represents one or more substituents selected independently from the defined group of substituents preceding Z ira.

The detected by R _1, R ₂ and R in formula 1 bicyclic ring systems can follow by the generalized formulas 3 ^ and displayed 4:

A ₂ j A

ζ ζ

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

- HO-

N-oxides and the sulfinyl, sulfonyl, selenium oxide and phosphine oxide-containing ring systems. Selected carbon atoms contained in A ₂ and A ₃ may attach carbonyl, thiocarbonyl, substituted or unsubstituted imino groups or substituted or unsubstituted methylidene groups.

Bicyclic ring systems represented by Y ₃ and Y ₄ , which are linked together in formula 1_, may be any of the bicyclic ring systems of R ₁ , R ₂ and R ₃ positioned correspondingly in formula.

With respect to the structures covered by Formulas 3 and 4, the following is noted:

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

(b) When B ₂ J but not B ₃ , is nitrogen, 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 ₂ 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 ₃ contains a carbon atom bearing a carbonyl, thiocarbonyl, imino or methylidene group, it must form together with B ₂ and B ₃ a cyclic compound having at least four members.

(e) When an annular double bond to one of the two rings shown in Structural Formulas 3 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

- 91-

(f) When a group A ₂ or A ₃ is bonded 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 will be understood that the bicyclic ring-like radicals defined for the interconnected R ₁ , R ₂ , R _3, and Y ₃ and Y. may be spirocyclic ring systems and are not limited to the fused-together bicyclic structures of Formulas 25 and 4 , Spirocyclic ring systems may be saturated or unsaturated, carbocyclic or heterocyclic compounds and may be independently substituted by one or more substituents Z as defined above *

Polycyclic ring systems, i. greater than 2 rings by R

1'

and R ₃ in Formula 1 can be fol

are represented by the generalized formulas j5, 6_, 7 and S_:

-HZ-

7 572

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

and A ₇ can un

and B _{7 is} 1 to 11 carbon atoms

The ring-forming elements of A ₄ , A ₅ , depending on B ₄ , B ₅ , contain, they may contain a combination of 1 to 10 carbon atoms and from 1 to 3 heteroatoms, which are independent of N, 0, S, P or other heteroatoms or may contain 1 to 3 heteroatoms alone. Ring-forming heteroatoms can 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 can sometimes be defined as a bond. Selected carbon atoms contained in A ₄ , A ₅ , A ₆ and A ₇ may attach one or more carbonyl, thiocarbonyl or substituted or unsubstituted imino groups.

In structural formula 8_ are the group Bg, B _G, and B _{10 is} 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 Ag, A _g and A ₁₀ represent ring-forming atomic chains which, together with 1 from the groups B _Q , B _g , B ₁₀ and B ₁₁ , can contain 0 to 2 double bonds.

The ring-forming elements of the groups Ag, A _g and A ₁ Q, independently of the groups Bg, B _g , B ₁₀ and B ₁₁ , may contain from 2 to 10 carbonatorae, may contain from 1 to 10 carbon atoms in combination with from 1 to 3 heteroatoms independently under N, O, S, P or other heteroatoms can be selected, contain or may contain 2 to 3 heteroatoms alone. Ring-forming heteroatoms can in some cases attach oxygen atoms, such as in the aromatic N-oxides and in the sulfinyl, sulfonyl, selenium oxide and phosphine oxide-containing ring systems. Selected carbon atoms contained in the groups A _g , A _g and A ₁₀ can attach one or more carbonyl, thiocarbonyl or substituted or unsubstituted imino groups.

It will be understood that the polycyclic ring systems defined for the interlinked R ₁ , Rp, R, and Y ₃ and Y ₄ may be spirocyclic ring systems, rather than the fused polycyclic structures of formulas J5, 6>, 1_ and are limited. Spirocyclic ring systems may be saturated or unsaturated, carbocyclic or heterocyclic, and may be independently substituted by one or more of the substituents defined for Z above.

Polycyclic ring systems represented by Y ₃ and Y ₄ , which are linked together in formula

mel I ^ correspondingly positioned polycyclic ring system of R ₁ , R ₂ and R ₃ 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_, 1 £ and _11 as follows:

\ T ^A 13 A ₁₂ / Z

9 12 II

wherein B ₁₂ and B _{3 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 May contain double bonds. The groups Z represent one or more substituents which have been independently selected from the group of substituents defined above for Z (n).

The ring-forming elements of A ₁ , A ₂ 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 ₃ , A ₂ and A _{3 is} a single heteroatom, the other two groups must contain two or more ring-forming atoms. A second requirement is that when one or both B ₁₂ and B _{13 are} nitrogen, the groups A ₁₁ , A ₁₂

and A ₁ , at least two saturated ring-forming atoms must contain.

Ring-forming heteroatoms can in some cases attach oxygen atoms, such as in the sulfinyl, sulfonyl, selenium oxide and phosphine oxide coraponents. Selected carbon atoms contained in A ₁₁ , A ₁₂ and A ₁₃ may attach one or more carbonyl, thiocarbonyl or substituted or unsubstituted imino groups.

Bridged bicyclic structures represented by Y ₃ and Y., which are linked together in Formula 1 , can be any of the bicyclic bridging systems of R ₁ , R ₂ positioned in Formula J. and R ₃ .

It is readily apparent that formula _1 covers a wide variety of malonic acid derivative compounds. Illustrative Malonsäurederivatverbindungen within the scope of formula 1 ^, which can be used for crop improvement are listed in the following Tables 1 to 11.

Table 1 Representative malonic acid derivative compounds

O

, Il U

Ry-C-CH ₁ -C-NH

3-fS 3-fS 3-fS 3-f-5 3-f-S3 ³ " ³

^3Cf 3-3-Cf ₃ --ia ₃

3-f-4 3-f-4 3-f-4 3-f-4 3-f-4 3-f-4 2-f-4 2-f-4 2-f-4 2-f-4

-Cl-ClClBrBrS-ClS-ClS-BrS-BrJrBtCl Cl Cl -Br Br Br Ta Cl-S-Br Cl-S-Br

OCM.

I '

2-f-4-Br-S-Cl 2-f.4-Br-S-Cl 2-f-4.S-Br ₂ 2-f -. _'I-8r?

2.4-CI-5-f 2.4-CI -S-f 2-Cl-4-8r-S-f

2.4-ByS-r 2-Br-4CI-5-f 2-Br-4-CI-Sf 2 -CH ₃ -4-CI-5-f 2 CH ₃ -4-CI-Sf 2-CM ₃ -4 -Cl-2-Sf CM -4-Br-5-r 2-CH ₃ -4-Br-Sr-CH 2 -4-Br-Sf

OH

OH OCH 0 »* OH

OCH

-0-n-t - «- OH OCH OH

OH

OMj OH

OK

O

R ₁ -C-CH ₂ -CNH- / '

2-CI-4-Cf O 2-Cf 0-4-Br 2-CM -4-Cf Cf 0-2-CH ₃ -4-I 2-F-4-Br-Il.S,

3-8r-4-CI 2.4-CI

OCH 2 2 2 3 S 1 S K "CH 0-n ON * H -C H H OC OC 3 I H, OCH S OC

Table 2 Representative malonic acid derivative compounds

O O

, α κ '

Rg-C-CM ₂ -C-NH-

OCH CH OH OCM CH OH

OCH CO C H

OCH CH SCHOCH CH SO CH OCM CH SO CH OCH ₂ CCH ₃

OCH ₂ CCH ₃ , OO Λ ii > • O OCH (CH 2 IC 2 H 2 OCHCH Rg-C-CM ₂ -C OM.C (CH ₃ » ₂ 2-CH4-Br 21-4-Br 3.4-Cl ₂ 2-CH4-Br4 Cl. 2.4-Br : 2.41S-C1

3-F-S-8r

2-CH4-Br2-CH4Br-S-Cl 2-1-4-Br

3.S-Br 3-Br-S-Cl

o-N.C.:

CH ₃ -SCH ₃ CH ₃

OCH CH ₂ HCOCHOCH ₂ CH ₂ OC-MHC ₂ Hj

^ OC ₂ Hj OC ₂ Hj

OCH ₂ P 0

OCH ₂ CH ₂ P '- 0

OCH ₃ OCH ₃

2.4.Ct "

2-CH ₃ -4-ar 4-Br 4 Ci 3.4- *. ₂

2.4-Cl ₂

2-CH ₃ -4Br 4 Cl

2-Ϊ-4 Cl ₃

2.4-Cl ₂

0CH, COHH,

OCH ₁

OCH ₃

3.4 Cl ₂

3. S

Table 2 (Forts,) Representative maleic acid derivative compounds

SCH CH f / ^ ' / ⁰ vs 3-ir-S-Cl OCH CM SCH * 2 J O Vs * ^ * ² * ^χι ν ₅ θ HHCH CH OH 3 Cl-S-Cf ₃ NHCH CH OCH CH SCH OH HMCH ^? CO ² C ° 2 ² OCH CH SO CH CH OH ι NHCH CH OCH CH C-H 3-Br-S-Cf 0-C (CH) C-N 3f 4-8r OCH CH OCH 2.4-CI CC J 4 cl OCH ₂ CH ₂ N · J 3 f-S-Cl OCH (CH ₃ ) CH ₂ SC ₂ H ₄ 3 - "- 4-Cl OCH COCH 2-f-4.5-CI ₂ OCH CM 2-F-4-Cl-5-8r OK, C (CH 2 J-CO C H 2-F-4-Br-5-CI Ö-CH SO HH 2f-4.S-er ₂ O-CH SO, "HCH 2.4 Cl -S-f O-CH _? SO M (CH) 2Cl-4-er-S-f S-CH CH SCH 2.4-Br ₂ -Sf S-CHCO ₂ C ₃ H, 2 Br 4 CIS f 2CH 4Cl-Sf 2 CH 4-8r-Sf

2-F-4-1 3-8r-4-Cl 2-Cf β-4-f 2 -CH ₃ -4- »f 3 -f-4-Cl 3 .S-Cl ₂ 2 -CH 4 βΓ 2-f-4- »r 2.4-» r,

Table 5 Representative malonic acid derivative compounds

R ₁ -CCC-KH-

ci 2-CH ₃ -4-9r 2.4 βΓ H 4-Cl 2-r-4-Br • r 2.4-Cl ₂ 2-F-4Cl H 3. S-Br 3-C 1-S-Br br 3.4-Cl ₂ 3.4-Br -C-I - ~~ \ S ί * 1 * · 2 CI-4-8r 2 2-Cl-4-8r Γ 2-CH4 Br f H CH ₃ O- H H H ν-

OCH OH ~

^a S ^H s

OCH CH OCH

OCH

OCH (CH) C ^

CH.

2.4-Br,

II.-C-C-C-I

CH .CH- H 3.S-Br ₂ ".C H 2-C « ₃ -4-8r K.C- H 2.4-Cl ₂ K ₁ C- ^CH 3 3-f 4- »r o ₂ «. Cl 2.4.S-Cl H.C- br _ * 3-8r-5-f HlUHH- '' H 3JS- (Cf ₃ J ₂ HC-C- H 2.S-CI ₂ ^C 2 ^M S f 3-Cl-S-Cf CH 0- ^CM 3 4br

OH

OCH

OCH COHHOCH CH OHOCH CHSCH, --- -2- -; - "- 3-

OCH _? COCH OCH.

4-Cl

^CH 3 HO-

2-CI-4-Cl

2 CH 4 BrOH

Table 3 (Forts,) Reprasentatxve Malonsäurederivatverbindungen

ι '.

1'

10

CH ₃ O-MOCM CMjCO-CH CO- -CMO -CMO

CH ₃

br

^C 2 ^H 5 Jr

trip

HIGH H

^CH 3

he

Cl Cl Br CH.

2-Cl-4-Cf 2-Cf ₃ e-4-f 2 -CH 4-Cf Cf

J- ^ Br-4 ^ C J "2-f-4 I-

4-Br

2-Ο-4-8Γ 2-CM ₃ -4-Cl 3.4-Br ₂ 4 Cl 2 -CH 4-Br

OH

OC, H -? j

Üch

OCH SCH ₃ OC ₂ H ₅ OCH ₃

OCH

Hf-C-C-C-Ntl O

CHjCOKH- - 1 H HCONH- H MCI'HjN-   , "'H' -Q-CHj-O- -S-CHjCHjS- CH ₃ O H CH.e , , H CM ₃ S M chjo M CjHjOCO CH, CHjS ' , ^CH 3 CH ₃ SO CH ₃ CH ₃ SO ₂ H CH ₃ SO. t 3

2-f-4, -lr

J-CHj.4-lr2-CHj-4- »r

3.S-Ir J-Sr-S-Ct 3-er-J-F ', 4-Cl

2-f-4-8r 2 -CHj-4-lr

? -CHj-4 »rOCH ₃ SCII-CH ₂ OCMj

OC ₂ M ₅

OC ₂ M ₅ 0-n-CjH,

OC ₂ M ₅

OC ₂ M ₅

Table Representative malonic acid derivative compounds

LJ U OS O)

I i i S

S3 S3 W - W -

CD W OD -v «r U

(X X is S UXZUSZXW

aooazoao

η f. n

SXX JUUSXXXX

XXXX

Table 4 (Forts,) Representative malonic acid derivative compounds

U U

I i

• aj. N ι ι - »»

_v ι «α ο ι ο ι» »ι"

Sir »nnn» i '

, r * ι · ί? - XXWu. W

I Ο «Ο

ι · _λ "^

ο ο

• «Χ> λ

Sl-I M X X X O O O O * <

: · Χ χ χ

χΐχ ΰ χ

! I i ι ιί '

XX χ '

χ 5

Kuuxx

Table 5 Representative malonic acid derivative compounds

M λ »<v

N N Pl

- W CO U U β ♦

W «te <-) S3 'β UWU

nt ίΜ^! fs

u £ u Χω

"9 S S

S I S

χ, ^Ν γ

XXXX

XXX

SZ UU

XXXXXUX

Table 5 (Continued) Representative Maoic Acid Derivative Compounds

ν «

(M rt (V «r

§ I

T '

 to DU

if cn rv η m cw λ * <m fv fv

ι ι τ τ

- »O O O

- ncii-fr

X X k »- (N

υ, u u w u

χ · »ό χ

UZXZXUXX OQOOOOC30

X S'-X O

UXUX

XXXXXX

UUXSXXX

WXSSSS =

X S

UXX ^ XUUUX XX

UuX.ω UU

Table 6 Representative malonic acid derivative compounds

I ") W XW

X Of «I * #

wxo »w o s

OO Vt X-.Vl-O

N N (MU Π (V Γ

X X X X X X 'X WWWWWWW

CV (V (V IV w <V 1

XXXXXXX

O O O O O O

t <v pm e

.8 I

O X

S S

a χ χ

JWW

f * (N.r *:

χ -ΰ

W W O Vt

O X

x ~ ä

I W W

fV fV

W ·

^ (V. W

ι L. V O

r> es * mn

U ♦ CD U W

(ν <v rl (V rg

XXXX

χ -χ χ

WWZXWX

Table Representative maleic acid derivative compounds

U <N

IMX X U

f "> u in> n

X INX X UOU (N I "

o m α u χ

(N (N Λ. IN U

s χ χ ο 2

UUUUUU

_ S y ό

u m \ /

- 'W. *

3 ~ ή

V ^s i

xx u

i 1, IN X IN O U X X x ~ ä H CONH i IN X : h ₂ o ₃ χ fN X 1Λ x ~ x ~ X IN X X O O ο α α O

IN w »

S!

χ S

n _ - η

in in r * (N

Table 8 Representative malonic acid derivative compounds

(7

(7

-C-C-Υ "R " OO

14

OH OH OH OCH

2,4 Br ₂

28r-4-C'H 0-

2

-CH (CH ₃ ) CH--

«HCH« HCH CH OH

OCH ₃

OCH.

2.5

* (4 ClC 6 ^H 4 ° * 5-Br ₂ 2.4 Ci ₂ 2-Cl Br ₂ - 4 · Br Λ ⁰ 2 CH 2.4 5-CI 2-Br-S-C

3,4-Cl

^M Il B "O

2f_

14

IS

oh:

~ WHCH.CH; 8CH_ ---

₂ 2-8r-4CN

4 cl

3.4 Br 3-er-S-CI 2-Cf -4-Br

OCH.

Table 9 Representative malonic acid derivative compounds

30

CH ₃ N ₂ CM.C-

^ε Λ

CH O-CH 0 N-C-

H 3 H H H 3 CH br H 3 ° CH H H CH br

IS

^CH 3 CH.

0 s

S S 0 S 0 S 0 0 S 0 S 0

On-CH

OH OCH,

OC ₂ H ₅ NHCH.

OC ₂ H ₅ OCH

2. * Br ₂ 2 -Cl-4-CH 0-

2-Cl-4-8r 3.5-Br 2.4 Cl 2 f-4 Cl

2-Cl-4-Br 2.4 Cl 4 Br 2 Br-4 CN

Table 10 Representative malonic acid derivative compounds

34

H 3 H H ^CH 3 H H c. ^M , - H H ^CH 3 H H ^CH 3 H H ^CH 3 H CH CH H CH. H H H H H H H

32

«NHH NH NH NH NH NH NH NH

CH.

0 s

NH NH MH

OC ₂ H ₅

OC ₂ H ₅

OCH ₃

OC ₂ H ₅

SCH ₂ CH ₂ OCH ₃

OCH CH OH

OCH OH

OC ₂ H ₅ OC ₂ H ₅

2-CH 4-llr

2-l-4-8r

2-F-4-C1

3.4 8r

2 CH -4 Mr CH 0 4. Ί 5 Cl 3. 4 Cl Cl / 3 f-4 Br Third 4 Cl M rl 2-0 ^ -4 Iu 2

4 cl

Table 10 (continued) Representative malonic acid derivative compounds

^CH 3 ^CH 3 ^CH 3 ^CH 3 ^CH 3 ^CH 3 ^CH 3

CH ₃

CI

HH

NH

HH

RH

HH

HH

HH

HH

NHOH OH OCH ₃

OCH ₃

0CH _? CN

OCH CH OCH-

^0C A

2.4 Cl ₂ 3.4 Br 3-Cl-S-Br

2-CF 4 -flr 3-Cf ₃ -S-Cl

2.4Cl ₂ 3.5 Cl ₂ 3.4 Br 2-8r-4 CN 2-CH 4-Br 2.4 Br ₂ 2 CH 4-Br

34

-S-CH.

Cl

Sr

₃ CH ₃ O

H Cl

HH NH NH

OC ₂ H ₅

OCH ₃

OCH ₃

OCH ₃ SC ₄ H ₅

OCH.

4-C1

3.4-Cl ₂

2-F-4-C1

3.S-Br ₂

3.5-CI ₂

2,4-Br ₂

Table 11 Representative malonic acid derivative compounds

cc

O O

36

35

Ιβ

JO.

sr α

C O

NH

Cl

(Of "

Cl

Y '

18

egg

CH.

br

H-C

CH,

SCII CHOCH

OC "H _S

Cl

OCH CIUCII

DWQ

Table 11 (cont.) Representative malonic acid derivative compounds

ο o

V't '1' t ' W

^T 3t 37 ^T 35 18 1?

OCH

CH H HH 0-n-C.H

It is believed that the subject compounds set forth in Tables 1 to 11 above are examples of the malonic acid derivative compounds which can be used to increase the yield of the present invention. However, the invention is not limited only to the use of these compounds, but also includes the invention the use of the malonic acid derivative compounds of formula 1-1 above.

The novel malonic acid derivative compounds according to the invention can be represented by the following formulas:

^R 6 - ^Y 12 - ^C - ^CH 2 - ^C in which:

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 , Alkylsulfonylaraino, 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); and

R-ammonium, alkylammonium, polyalkylammonium, hydroxyalkylammonium, poly (hydroxyalkyl) ammoniura, an alkali metal or an alkaline earth metal or substituted or unsubstituted hydroxyalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkylaminoalkyl, dialkylaminoalkyl, aryl, mercaptoalkyl, alkylthioalkyl, arylthioalkyl, aryloxyalkyl, alkylsulfonyl

- es-

alkyl, alkylsulfinylalkyl, acylalkyl, aroylalkyl, dialkoxyphosphinylalkyl, diaryloxyphosphinylalkyl, hydroxyalkylthioalkyl, hydroxyalkylsulfonylalkyl, alkoxyalkylthioalkyl, alkoxyalkylsulfonylalkyl, poly (oxyalkylene) alkyl, cyanoalkyl, nitroalkyl, alkylideneamino, carbamoylalkyl, alkylcarbamoylalkyl, dialkylcarbamoylalkyl, aminoalkyl, acylaminoalkyl, acyloxyalkyl, alkoxycarbonylaminoalkyl, cyanoaminoalkyl, carbamoyloxyalkyl, Alkylcarbamoyloxyalkyl, dialkylcarbamoyloxyalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonylthioalkyl, aminosulfonylalkyl, alkylaminosulfonylalkyl or dialkylaminosulfony! Alkyl;

^Y 15

^R 8 - ^Y 14 - ^C - ^C - ^C ! IH

• o

in which represent:

Zp is an independently substituted or unsubstituted halogen, haloalkyl, polyhaloalkyl, polyhaloalkoxy, alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfinyl, aryl, aryloxy, arylthio, arylsulfonyl, nitro, cyano, dialkoxypropyl, acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, Acylamino, sulfonylamino, alkylsulfonylamino, acyloxy, alkenyl or -CH = CHCH = CH-;

η is a value between 0 and 5;

^Y 13 ^{is S} ° * ° ^ ^{he "wc"} "is hydrogen or alkyl, R _g ^NR g;

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, formylamino, hydroxyalkyl, haloalkyl or polyhaloalkyl, provided that Y is alkyl, then

Z _{2 is} not a halogen or polyfralcoalkyl in the para position and that at least one of Y ₁₅ ^ur > d Yg is other than hydrogen;

Y ₁ and Yg may be linked together to form a 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 can; and

R _Q is hydrogen or R _c ; ^Y 20v / ^Y 19

^R 10 " ^Y 18""C ~ ^C ~ 0

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 = CHCH = CH-;

η is a value between 0 and 5j

Y ₁₇ is O, S or NR ^ ₁ , wherein R _{11 is} hydrogen or alkyl;

Y ₁₈ is 0 or S;

- (ο B -

Υ- and Y ₂₀ are independently hydrogen, alkyl, alkoxy, alkylthio, halo, haloalkyl or polyhaloalkyl; or

Yg and Y ₂₀ may be bonded together to form 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 bridged ring system, which may be saturated or unsaturated; and

R ₁₀ is hydrogen or R _&g; and

R ₁ -YC - C CY ₂ - R ₂ (XV)

H Il

^Y 5 ^Y 6

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 Y ₂ are independently a substituted or unsubstituted heteroatom;

Y and Y ₄ are linked together to form a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or nonaromatic ringystera, a bicyclic aromatic or nonaromatic ring system, a polycyclic aromatic or nonaromatic ring system, and a bridged ring system that is saturated or may be unsaturated; and

Y_ and Y ₆ are independently oxygen or sulfur; wherein the permissible substituents for the abovementioned formulas (i) to (iv) are Z as defined above. ·

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

γ ^{Y Y} 25 ^Y 24 _γ

^Y 26 I | / ^Y 23

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, aryl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino, sulfonylamino, alkylsulfonylamino, acyloxy, alkenyl or -CH = CHCH = CH-;

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 ₂ is hydrogen or R ₅ ; or

^Y 28 O Il C ^Y 34 ' ^Υ 32 \ / C 30 29 0 Il • C · (Vi) / ^R 14- \ / C / N / Λ \, - C / 31 " ^Υ 27" / \ / C

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 ₂₇ is O, S or NR ₁₅ , wherein R _{5 is} hydrogen or alkyl;

Y ₂₈ is O, S, NH or N (alkyl);

^Y 29 ' ^Y 30' ^Y 31 * ^Y 32 * ^Y 33 ^{and Y} 34 ^are independently hydrogen, alkyl or halogen;

§ vss

and R ₁₄ is hydrogen or

O ι 1 Ο

^R 16 "" ^Y 36 " ^CCC ~ ^Y 35

in which represent:

Zg 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 ₃₅ is O, S or NR ₁₇ , wherein R _{17 is} hydrogen or alkyl;

Y_ _s is 0 or S; and

R " _c is hydrogen or R _c ; Ib o

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 JL and the intermediates used for 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 of the above formulas (i) to (vii) which can be used in the process of this invention can be prepared by reacting appropriate starting materials according to conventional procedures described in the art, 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 ♦

( ² l) n

0 (ζΛ _η

Λ ^χ > ^η

Acid,

acceptor "" Y /

I ^ * ^R 6 "" ^Υ 12 ~ ^C " ^CH 2 ~ ^C ~ ^Y

Scheme I

wherein Zi η, Y "", Υ _ΛΟ and R _{c have} the meanings explained 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, Oohn Wiley and Sons, New York, p · 486 described. In the Schotten-Baumann process described therein, cold aqueous sodium hydroxide is taken as the acid acceptor.

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

ssb »a,S ₁ ^ g tea

16 »7 15

^R 8 - ^Υ 14 - ^C - ^C - ^C - ^CI * ^HY 13 Il II

O O

Acid ^YI \ / ¹⁵ ^ "

R ₈ -Y ₁₄ -CCCY ₁₃

Scheme II

wherein Z ₀ , η, Y ₇ , Y-, _A "'Y-, = # Y _1fi and R _{0 have} the meanings explained above. 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, GH, "supra. above, described according to the known Schotten-Baumann method.

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

γ γ

^T 20/19

^R 10 - ^Y 18 - ^C - ^C - ^C - ^CI V ^HY 17 0 0

^Y 20 ^Y 19

Acidity H

acceptor J /

TTT ^ ^K 10 " ^Y 18" ^υ ~ ^c ~ ^L " ^Y 17 -HCl H"

0 0

Scheme III

wherein Z, η, Y.-, Yq »Y _1q * Y _O n ^{and R in the 0D} en have explained meanings. Reactions of this general type for the preparation of the malonic acid derivative compounds of formula (iu), including the process conditions, are described by Richter, GH, s. above, described according to the known Schotten-Baumann method.

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

R ₁ -Y ₁ -CCC-CI ♦ HY ₂ - R ₂ II

^Y 5 ^Y 6

acid acceptor

+ R ₁ - Y ₁ -CCCY ^ -R ₉

HCl II

^Y 5 ^Y 6

Scheme IV

wherein R ₁ , R ₂ , Y ₁ , Y ₂ , Y, Y ₄ , Y ₅ and Y _{6 have} the meanings explained above. 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, described according to the known Schotten-Baumann method.

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

- -Fl-

γ γ

_γ 25 24 _γ ^Υ 26 yy ^Υ 23

C-C

R ^ ₂ ~~ ^ ₂₂ - C - "C" ~ C -

, O

♦ HY

acid acceptor

-HCl

* R ₁₂ -

YY ^Υ 25 ^Υ 24 _γ

²⁶ i I

C-C

Y /

Scheme V

wherein Z ₄ , η, Y ₂₁ , Y ₂₂ , Y ₂₃ , Y ₂₄ , Y ₂₅ , Y ₂₆ and R _{12 have} the meanings explained above. Reactions of this general type for the preparation of malonic acid derivative compounds of formula (v) including the process conditions are described, for example, by Richter, GH, s. above, described according to the known Schotten-Baumann method.

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

γ γ ^Y 32 ^Y 31

33

Cp

^R 14 " ^Y 28 ~ ^C

30

Y ₂₉ I

c - egg

acid acceptor

-HCl

^R 14 - ^Y 28

^Υ 32 ^Υ 31

\ / C

C C

30

29

C · - "

N "

Scheme VI

wherein Z

η, Y

Y ₃₄ and

₅ , η, Y ₂₇ , Y ₂₈ , Y _2g , Y ₃₀ , Y ₃₁ , Y ₃₂ , Y ₃₃ , have the meanings explained above. 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, GH, s. above, described according to the known Schotten-Baumann method.

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

^R 16 " ^Y 36 '" ^C

C-CI

HY

35

Acid acceptor -HCl

Scheme VII

wherein Z _c , η, Y -, =, Y, _c and R _c the above Bedeuo ob oo Ib

have. 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, G.H., supra, according to the known Schotten-Baumann method.

In addition to the above-mentioned process, for example, other illustrative methods that can be used for the preparation of malonic acid derivative compounds of formula _1 and the intermediates necessary therefor are described in the following references: Breslow, DS et al., Oour. Amer. Chem. Soc. j56, 1286-1288 (1944); Svendsea, A. and BoIl. PM, Oour. Org Chem 40 , 1927-1932 (1975); Sen, AK and Sengupta, P., O. Ind. Chem. Soc. 45, (9), 857-859 (1969); Thiers, R. and Van Dormael, A., Bull. Soc Chin ». Beig. 61, 245-252 (1952) _; Brown, RFC, Austral. Dour, of Chem. 8_, 121-124 (1955); US-F = S 3,951,996; British Patent 1,374,900; Chiriac, 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 _o, Paul, Org. Syn. Coll. Vol. V, 381-383 (1973), Oohn 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), 2o Edition, John Wiley and Sons, New York; Staudinger, H. and Becker, H., Berichte 50, 1016-1024 (1917); Purrington, ST and üones, WA, CJ. Org. Chem. 48, 761-762 (1983); Kitazume, T. et al., Chem. Letters (1984) 1811-1814; Wolff, IA et al .. Synthesis (1984), 732-734; Zambito, AD and Howe, EE., Org. Syn. Coll. Vol. V, 373-375 (1973), John Wiley and Sons, New York; and Curing, WH et al., Org. Syn. Coll. Vol. V, 376-378, Oohn Wiley and Sons, New York ·

Further illustrative methods that can be used to prepare malonic acid derivative compounds of Formula 1-1 and the intermediates required therefor are described, for example, in the following references: Rathke, M.W. and Cowan, P.O.,. O. Org. Chem. 50, 2622-2624 (1985); Fönes, W.S., Org. Syn. Coll. VoI, IV, 293 (1963), Oohn. Wiley and Sons, New York; Gompper, R. and Top'fl. W., Chem. Ber. 95, 2861-2870 (1962); Gompper, R. and Kunz, R., Chem. Ber. 99, 2900-2904 (1966); Ono, N. et al., 3rd Org. Chem. 50, 2807-2809 (1985); U.S. Patent 4,154,952; Blankenship, C. and Paquette, L.A., Synth. Comm. _14, (H) * 983-987 (1984); Baldwin, O.E. et al., Tet. Lett. 26, (4), 481-484 (1985); Kawabata, N. et al., Bull. Chem. Soc. Ορη .. 55., (8), 2687-2688 (1982); Bodanszky, M. and du Vignaud, V., O. Am. Chem. Soc. 8jL, 5688-5691 (1959); Neelakantan, S. et al., Tetrahedron .21, 3531-3536 (1965); U.S. Patent 4,020,099; OA-PA 148,726 (1979); Fuson, R.C., Advanced Organic Chemistry, p. 202 (1950), Oohn Wiley and Sons, New York; Duty, RX., Anal. Chem. 49, (6), 743-746 (1977); Korner, G., Contradi, Atti acad. Lincei 22, I, 823-836 (CA £, 73 (1914)); Schimelpfig, CW., 0. Chem. Soc. Perk. Trans. I, 1977 (10), 1129-1131; Kim, Y.S. et al., Taehan Hwahak Hoechi, 18, (4), 278-288 (1974); DE patent 2,449,285; U.S. Patent 3,962,336; and U.S. Patent 3,992,189.

Co-pending US Patent Application Serial No. (D-15328), filed on even date, describes the use of malonic acid derivative compounds of formula I "_1" to retard plant growth. 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 JL contain. These two applications are incorporated herein by reference.

It has been found that the malonic acid derivative compounds of formula 1 significantly increase the yield compared to untreated crops under the same conditions. In addition, the malonic acid derivative compounds according to the invention are essentially not phytotoxic to growing plants.

As used herein, an effective amount of a malonic acid derivative compound for increasing crop yield refers to an effective yield increasing amount of the compound sufficient to increase the yield. 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 climatic 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 necrosis. 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, as described in detail below.

The malonic acid derivative compounds encompassed by Formula I can be applied 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 either in 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-phytotoxic solvent such as acetone, xylene, nitrobenzene. Cyclohexanone or dimethylformamide and dispersion of the active constituents in water with the aid of suitable emulsifying and dispersing surfactants.

- '' 51 / Oil.

be prepared medium. The choice 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, in accordance with the desired dispersion of the active ingredient in the spray, to use as little of the agent as possible, so that the active ingredient, after being applied to the plant, will not be re-emulsified by rain and released from the spray Plant can be washed off. Nonionic, anionic or cationic dispersing and emulsifying agents may 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 compositions, the active ingredient is dispersed in and on a suitably divided solid carrier such as clay, talc, bentonite, diatomaceous earth, fullers earth and the like. In the formulation of the surface-active powders, both the aforementioned dispersants and lignosulphonates may be included.

As the required amount of the active ingredient of the invention, between 1 and gallons or more of a liquid carrier and / or diluent or between 5 and 500 pounds of an inert solid carrier and / or diluent may be applied per acre to be treated.

The concentration in the liquid concentrate is usually between 5 and 95% by weight and in the solid formulations between 0.5 and 90% by weight. Generally, satisfactory sprays or dusts for general use contain between 0.001 and about 100 pounds

the active ingredient per acre, preferably between 0.01 and about 15 pounds of the active ingredient per acre, and more preferably between 0.1 and about 5 pounds of the active ingredient per acre.

The formulations useful in the practice of the invention may also include other optional ingredients, such as stabilizers or other biologically active compounds, as these 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 agents, 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 1-1 are preferably applied to plants and crops under substantially average or normal growth conditions. The malonic acid derivative compounds of the present invention may be applied during the vegetative growth phase of the plants or the reproductive growth phase of the plants to achieve an increase in crop yield. For some crops, it may be desirable to include the malonic acid derivative compounds in the reproductive growth phase, such as e.g. at the beginning of flowering, at the time of fruiting or at full flowering time. In other crops, it may be desirable to apply the malonic acid derivative compounds in the vegetative growth phase. The application time generally depends on the particular crop to be treated.

The compounds are useful for agriculture, horticulture and related areas to increase crop yield.

An increase in crop yield can be achieved e.g. due to various effects on plant growth, such as increased branching (more reproductive sites), early budding (fruiting) approach, increased flower bud and inhibition of flower (flower and fruit) separation at the beginning of reproductive development of the plant. As used herein, an increase in crop yield refers to an increase in agricultural raw products, such as harvestable yield, e.g. Bushel seeds, cotton bales and the like. It is also possible that a treated crop brings a higher harvestable yield compared to an untreated crop, but that the total biomass of the crop being treated may be lower.

However, as used herein, harvestable yield includes the total biomass of the crop, such as. Bushels of corn per acre, and the like. By treating certain crops, such as alfalfa, with the malonic acid derivative compounds of formula _1, the nutritional value of the crop, for example total digestible nutrients (TDN), may also be increased.

As used herein, plants and crops generally refer to all crops cultivated in agriculture and horticulture, ornamental plants and grasses.

Examples of plants and crops that can be treated with the malonic acid derivatives of formula I by the method of the invention are, for example, corn, cotton, sweet potatoes, white potatoes, alfalfa, wheat, rye, rice, barley, oats, millet, dried beans, soybeans , Sugar beets, sunflowers, tobacco, tomatoes, canola, sloping fruits, citrus fruits, tea, coffee, olives, pineapple, cocoa, bananas, sugar cane, oil palm

-fo-

plants, woody shrubs, lawn grasses, ornamental plants, evergreen plants, trees, flowers and the like.

The malonic acid derivative compounds of the invention are effective in increasing crop yield. Such compounds have a great safety margin in that they do not burn or injure the plant or crop when used in an amount sufficient to produce an increase in yield, and they are weather resistant, including resistance to rain washing, resistance to deterioration ultraviolet light, oxidation or hydrolysis in the presence of moisture or at least resistant to such decomposition, oxidation and hydrolysis which would significantly reduce the desirable yield enhancing properties of the active ingredient or cause undesirable properties such as phytotoxicity. mixtures of the active compounds and combinations of the active compounds with other biologically active compounds or ingredients may be applied as desired, as highlighted above.

Exemplary embodiment . ,

The invention is illustrated by the following examples.

Example I

Preparation of ethyl 3-f (4-fluorophenyl) amino 3,3-oxopropanoate

In a nitrogen-purged, air-stirred

To the reaction flask were added 4.44 g (0.04 mol) of 4-fluoroaniline, 4.05 g (0.04 mol) of triethylamine and 200 mmol of tetrahydrofuran solvent, an amount of 6.02 g (0.04 mol) of ethylmalonyl chloride then added with stirring rapidly at room temperature, followed by a few milliliters of tetrahydrofuran was added "the temperature rose to 42 ⁰ C and triethylamine hydrochloride was allowed to settle. the mixture was then stirred at ambient temperature, filtering off the triethylamine hydrochloride, washed with solvent and dried, yielding 5, 2 g (0.04 mol) The solvent was expelled from the filtrate and the resulting purple solid was dissolved in methylene chloride, washed with 2N HCl (3 × 75 ml) and water (2 × 75 ml), then the solvent was evaporated was driven off to give a solid crude product Recrystallization from ethyl acetate-cyclohexane followed by flash column chromatography afforded 3.47 g (0.015 mol) of ethyl 3- [(4-fluorophenyl) aminoj3-oxopropanoate (compound 1) having a melting point of 68 ⁰ C to 71 C.

Example II

The compounds 2 to 76, which are listed in Table A, were prepared in the same manner.

Table A Representative malonic acid derivative compounds

O O

- C - CHp - C ""

Connection no.

substituents

R '

Z ¹ elemental analysis

Calculated

Found

melting point

2 CH 4-Cl 3 CH 4-CN 4 p vs JVs 6 ^C 2 ^M 5 3-Cf -4-βΓ) t j rl c j [4 C - "- * - !. 1-3 3-CH -4-6r 10 ^C 2 ^H S 3-cr ₃ U CH 3-CI 12 ^C 2 ^M S 3.4-Cl ₂ U CH 2 <-. (CHJ 1 «IS Vs · 3.4- (CHJ ₂ 2 -Cl-4-r 16 vs 2-Cl

H (CHJ NH NH-NH NH NH NH NH NH NH O NH H NH NH

56.36 62.06 63.66 47.6S 40.70 45.52 49.69 46.01 52.36 54.67 47.66 66.36 66.36 50.66 54.67

5.46 12.07 5.32 5.07 3.96 3.54 4.46 4.67 5.09 5.60

5.95 5.95 5.39 5.60

56.25 61.68 63.79 47.66 40.69 45.41 49.63 49.25 51.98 53.96 46.63 66.52 66.29 50.52 54.58

S.S3 S.09 6.57 4.14 3.24 5.26 5.67 5.24 4.53 5.33 3.66 7.00 7.26 4.18 5.11

5.21 11.99 5.34 S.08 3.97 3.56 4.96 4.65 5.22 5.86

P.76 5.90 5.19 p.

49-52 101-103

67-70

67-61

6 "-72

91-98 143-145

62-45

71-72.5 011 OU

98-19

68-70

66-71

54-51

Connection no.

Table A (cont.) Representative malonic acid derivative compounds

substituents

z ·

Z '

C - CH ₂ - C - V

Elemental analysis

Calculated

Found

melting point

^C 2 ^H S

4 -CH.

1" ^C 2 ^H $ 2-cr ₃ -4 ci 20 2.3-Cl ₂ 21 22 ! Ι "· * 23 24 ν! ' 3.4.S-Cl ₃ 25 2-CH4-Cl 26 27 "Α. 4-CH S-

MM "(COCI ₃ ): J 1.17-1.39 (t.3H). 2.33 (I. 3H). 3.4S (J.2H), - 4.07-4.42 (q.2H). 6.99-7.S7 (i ».4H). β.9-9.3 (br.H) ppm.

NHR (COCI ₃ ): J "1.15-1.46 (t.3H), 2.23 (J.fcH)

 2.50 (p.2H). 4.07-4.50 (q.2H), 7.10 (i.3H)

 β.37-β.7β (br 1.H) ppm.

0O B3

47-100

NH 46. S4 3. SB 4:52 46.68 3.71 4:47 58.4-61 NH 47.8S 4:02 5:07 47.84 4:05 5:07 72-75 NH 47.eS 4:02 5:07 47.98 3.99 4.93 66-68 NH 36.19 3:04 3.84 36.59 3.17 3.71 "S-t7 NH 56.37 5:52 5:48 56.76 5.72 5.26 "6-96 NH 42.54 3.25 4.SI 42.95 3.16 4.28 111-113 NH 56.31 5 ^ 52 5:48 56.00 5.67 5.21 103-104 NH 47.85 4:02 5:07 47.91 4:05 4.79 78-79 NH 56.69 5.97 S.S3 56.75 5.90 5:48 73-7S

Connection No. ₀

^C 2 ^H 5

^C 2 ^H 5 ^C 2 ^H 5 ^C 2 ^H 5 Vf ^C 2 ^H 5

Vs.

Table A (cont.) Representative malonic acid derivative compounds

substituents

Z '

J-CH ₃ OS-CI 4-1

4-nC H 0-2.4.5-C » ₃

2-C1-4-6r 2- »r-4-Cl

2-CH 0-4-Cl

Il

ρ _

Z *

- C - Y

Elemental analysis C 45.49 H 3.23 N C 45.96 Found· N enamel ^Yv Calculated S3.04 5.19 4:08 53.65 H 4:02 Point 39.66 3.63 5.16 39.30 3.23 5.14 ⁰ C NH 62.13 6.82 4.20 62.45 P. 31 4:08 NH 68.41 Eg 04 5:57 68.91 3.68 5.77 72-75 NH 66.42 8.20 5:32 67.18 7:03 5.86 86-87 NH 64.49 7:58 4:56 65.09 8.29 4:58 108-110 HH 42.54 3.25 5:01 42.40 8:35 4.77 100-101 NH 36.19 3:04 4:51 36.29 7.75 4:39 011 NH 41.21 ' 3:46 3.84 41.29 3:09 3.7? 66-68 NH 41.21 3:46 4.3? 41.59 2.93 4:35 82-83 NH 69.44 5:51 4.3? 69.75 3:42 4:55 104-105 NH 36.19 3:04 4:50 36.27 3.61 4:48 83-15 NH 43.44 3.65 3.84 43.49 5:51 3.68 78-80 NH S3.04 5.1S 4.61 53.38 3:33 3.95 81-83 NH 5.16 3.88 5.10 87-88.5 NH 5.23 64-67 NH 78.5-80 71-73

Table A (Forts) Representative malonic acid derivative compounds

C - CH ₂ -

Z '

Connection Nr,

substituents

R '

Z *

Elemental analysis

YV

Calculated

Found

melting point

O,

^C 2 ^H S

^C 2 «SC ₂ H ₅

C ₂ H ₅

2-CHJO-4S-CI ₂ 2 -CH ₃ -3.4-C1 2-r-4-CI 3-er-S-Cl 2 -CH 4 -8r '2-CO H-4-Br

2-CH ₃ -SS-CI ₂

2-CH ₃ -4.S-Cl ₂

2-C ₂ H ₅ -4-C1

2-CH, -3-Cl

3-HO4-C1

2-CH

2-CH

NH NH NH NH NH NH

NH NH NH NH NH NH NH NH

4,284.52 4.27 3,465.53

4.58 4.B3 5> 3i 4.37 4.27

41.31 49.86 50.90 41.26 51.59

4.64 4.62 4.56 3.67 5.41

NHR (OHSO d _& ): J 1.16-1.43 (t. 3H). 3:48

(P.2H). 4.06-4.7 (·, 4H). 7.S-8.7 ((· 3H) ppm.

49.67 49.67 S7.89 S6.37 46.08 6S.14 60.7S SI.33

4.N2 4.52 p.98 5.52 3.87 6.83 6.37 4.N7

4.83 p. 9.77 6.33 p.90 4.61

49.22 49.66 58.26 56.49 46.52 63.60 60.82 51.65

4.43 4.40 6.06 S.49 4.00 6.SI 6.28 4.92

4.59 4.69 p.21 4.14 4.17

4.45 p. 47. 9.43 6.12 p.84 4.33

95-98 90-93 66-69 78-80 91-93 151-154

116-120 134-135.

98-99 103-105

81-83

68-71

62-64 119-120

Table A (cont.) Representative malonic acid derivative compounds

Substituents

binding

No. R \ Z '

C - CH ₂ - C - V

Z ¹

Elemental analysis

Calculated

Found

melting point

si se st

HH HH NH

47.08

43.0;

61.18

4.S8 4.19 4.20

41.10 4l.eS 61.2)

4.22 4.31 4.94

4.61 3.72 4.14

90-9Z 132-135 86-87

J-

Cl

egg - // W

HO-CH ₂ -CH ₃

HH

S8.SS p.16 3.41

S8.91 5.23 3.29 Oil

4

⁰ l

HH

11.31 6.N6 3.96

TO.91 6.66 3.72 98-100

Table A (cont.) Representative malonic acid derivative compounds

R ' _a 0 - C - CH ₂ - C

Su Su bstituenten YV NH elemen L C H taranaj Lyse Found C H N enamel Ott Bond _t No. ^R ι ^Z 'l NH Calculated 68.15 5.84 4.69 Point OTI NH 68.22 5.13 46.85 3.91 4.12 η 18-80 , ..... "- - ' • NH 46.13 3.92 N 10:30 6-00 5:51 ⁰ C OTI "C ₂ H ₅ 2.5-Cl ₂ -S-CO CH HH 2.10 p.98 4.68 63.44 6:54 1:03 80-83 63 C ₂ H 2.3- (CH-CHCH-CH) NH 63.16 6:32 4.19 41.16 4:09 5:36 18-19.5 64 C ₂ H ₅ H NH 47.85 4:02 5:44 52.11 4:56 5.11 98-101 65 CH ₅ 3.4-Cl ₂ NH 52.31 4:39 6.16 52.20 4.21 11:14 96-98 66 C ₂ H ₅ ^4Cr 3 NH 52.38 "' 4.80 ' 5:01 46.33 4.16 4.91 93-95 61 C ₂ H ₅ 4-NO ₂ NH 46.11 4.23 5:09 41.56 5:02 99-100 MC ₂ H ₅ 4-Br HH 41.29 4.88 11:11 45.61 4:01 4.29 91-94 "C ₂ H ₅ 2-CH4-Br NH 45.31 4.10 4.90 48.35 4.88 4:56 50-53 10 CH CH OCH 2-CO CH -4-Br S 48.02 4.10 - 64.13 6.29 10.94 OTI "'A' 2-6r-4-CH NH 64.60 6.20 4:01 44.81 3.68 114-116 12 CH 4-C.n NH 45.06 3:44 4.61 48.10 4.85 4.11 109-110 13 ⁿ " ^C " ^H 9 3.S-Cl ₂ 48.02 4.10 10:16 61.41 6.18 30.5 14 CH 2-CH ₃ -4-Br 62.14 6.83 - IS C ₃ H ₅ 2-CH4-CH0 · 4.61 ^{16 C} 2 ^M 5 5:51

Oil = oil

Example III

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

To a nitrogen-purged round-bottomed flask was added 5.53 g (0.03 mol) of α-methyl-S-dichloroaniline, 3.18 g (0.03 mol) of triethylamine and 190 ml of tetrahydrofuran solvent. With vigorous stirring, an amount of 5.55 g (0.03 mol) 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-methyl-4,5-dichlorophenylaminocarbonyl) cyclopropanecarboxylate (Compound 77) having a melting point of 105 ° to 107 ⁰ C..

Example IV

In the same manner as in Example III, compounds 78 to 96 listed in Table B were prepared.

Table B Representative malonic acid derivative compounds

H ₂ C

R'O - C - C - C II

Ver SU binding No. ² 78 vs 79 vs ββ vs • I vs 82 vs • 3 C ₂ Hj • 4 vs • 5 C ₂ Hj 64 C H, 2 p • I C ₂ Hj ta C H 2 p a ' C H 2 5 90th vs "I vs 92 C ₂ Hj 93 vs 94 C ₂ Hj 95 vs 96 vs

substituents

Z ',

2.4.S-C

2-F-4-C1

4-Cl

4-Br

2. * - * «" 2-Cl-4-Br

2-Br-4-C1

3-Cl _T 4-8r

2-CH ₃ -4-Br-SC!

2-F-4-Br

4 -CH 2 -CH ₃ -4-Br

Elemental analysis 4 N C .69 Found N enamel Calculated 4 .16 46 .95 H 4.10 Point C H 4 .64 SI .21 3.99 4.12 ° C 46.3β 3.59 " 4 .64 51 .36 4:34 4:46 130-132.5 SI.61 4:34 4 .64 51 .92 4.S3 4:49 101-110 SI .67 4:34 5 .90 54 .IS 4:48 4.85 95-98 SI.67 4:34 4 .23 58 .18 4.11 5.16 105-108 S4.6S 4.S9 3 .49 SO .18 5.29 4:52 94.S-96 SB. 32 5.27 3 .58 40 .82 4.69 3.60 91-93 SO. 02 4:52 3 .58 39 .02 3:41 3:46 92.5-95 39.92 3:35 4th .58 40 .28 3:32 3.71 128-130 39.92 3.3S 4th .04 45th 89 3.61 3.90 91-92.5 39.92 3:35 4th .04 44th 16 3.98 3.80 102-103.5 4S.04 3.78 Third 04 45th 14 4.29 3.79 109-110.5 4S.04 3.78 4th 88 48th 81 4.20 3.86 95-96 45.04 3.18 6th 24 46th 54 4.14 4:02 113-116 46.62 4.19 4th 00 66th S2 4:01 5.80 119-121 41.29 3.97 10th 64 SI. 02 6:48 4:36 102-103 66.63 6:41 4th 85 65th 12 4:52 10.61 85 89 SI .67 4:34 29 51st 5:51 4.31 64-61 65.10 5:46 4.14 129-132 SI.SS 4.94 89-91

Example V

Preparation of 3-C (4-bromo-2-raethylphenyl) amino] -3-oxo-propanoic acid

An amount of 6.0 g (0.02 mol) of ethyl 3 - [(4-bromo-2-methylphenyl) amino] -3-oxopropanoate prepared in Example I (Compound No. 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 - [(4-8-rom-2-methylphenyl) -amino-3-oxopropanoic acid (Compound 97) as a white solid, mp 163 ° 165 ⁰ C.

Example VI

In the same manner as in Example V, compounds 98-109 were prepared.

Table C Representative malonic acid derivative compounds

R ' ₃ O - C - CH ₂ - C

Z ¹

Connection no.

substituents

R ¹

H H H H H H

H H H H H

3,

z ·

4-Cl 2-CH ₃ -4-er-5-Cl

2-F-4-8r 2-8r-4-CH ₃

2-8r-4-Cl2-C1-4-Br

2.4-Br

.2

3.4-Br 2.4-C1

3-C1-4-CH,

C H N Found C H N enamel Elemental analysis 50.60 3.77. 6:56 50.6? 3.80 6.3? Point Calculated 39.18 2.96 4.5? 39.36 3.14 4:44 ° C 32.08 2.09- 4.16 32.34 2:33 4:04 140-141 39.15 2:56 5:07 39.24 2:42 4.94 181-182 38.26 2.14 4.96 38.51 2.12 4.84 164-165.5 NHA (COCl ₃ V '0MS0-d _t \ l J · 2.27 (s.3H) , 3.4 (s.2H). 161-162 6.95-8.01 ( ".4H). 9.5-9.7 (br t. H) pp "·. 114-174.5 36.95 2:41 4.79 37.18 2.77 4.71 154-15? 36.95 2:41 4.79 31.10 2.60 4.76 32.08 2:09 4.16 32.27 2.23 4.13 159-161 32.08 2:09 4.16 31.96 2.22 4:08 165.5-167 157-159 14. 4

HH "(C0Cl ₃ / DMS0-d _t): J 2.49-2.64 (brj.H). 3.52 (p.2H).

7.17-8.24 (ι · .3H). 9.86-10.05 (br Ι.Η) ρρο.

«MR (C0C» ₃ / 0HSO-d _t ): J 2.30 (p.3H). 2.45-2.63 (br. P. H), 3.34 (j.2H).

7.05-7.86 (β.3H) _V. 10.04-10.23 (br Ι.Η) ρρβ.

Example VII

Preparation of 1- (2-methyl-4,5-dichlorophenylaminocarbonyl) cyclopropanecarboxylic acid

In a 250-ral round bottom flask, a solution containing 0.34 g (0.006 mol) of potassium hydroxide and 0.109 g (0.006 mol) of water in 80% ethanol was prepared. While cooling to a temperature of 0 ^° C. in an ice / NaCl bath and 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 The mixture was stirred under warming to room temperature over a period of 72 hours The mixture was evaporated in vacuo to give a white solid residue which was dissolved in water and extracted twice with ether acidified with 25% HCl solution to pH = 2 to deposit a solid which was taken up in ether and the acidified aqueous phase was extracted four times The combined ether extracts were dried over magnesium sulfate and evaporated in vacuo to give a This white solid was washed with water and dried in a vacuum oven to give 1.85 g (0.006 Moles) of l- (2-Methy1-4,5-dichIorphenylarainocarbonyl) cyclopropane carboxylic acid (Compound 110) having a melting point of 248 ° C to 251 ⁰ C.

Example VIII

In the same manner as in Example VII, the other compounds 111 to 128 which are listed in Table D below were prepared.

Table D Representative malonic acid derivative compounds

HO-C-C-C-NH

Connection no.

substituents

Z ¹

111 2-CK ₃ -4-Br 112 2. «. S-CI ₃ 113 2,5-Cl ₂ 114 2. <- C1 ₂ 115 2-F-4-C1 IU 4-Cl in 4-Br lit 3,4-Br ₂ IIS 3.5-Br ₂ 120 2-4-Br ₂ 121 2-Cl-4-Br 122 2-8r-4 ^ C1 123 ". 3-Cl-4-Br 124 2-t " ₃ -4-Br-S-C1 125 2-Γ-4-ΒΓ 126 ⁴ - ^CF 3 127 3.5-Cl,

128

3.4-Cl,

C 4t.34 H 4:06 3.31 N C 48.20 Found , 8.10 3.80 N enamel 42.82 2.61 .4.70 43.11 H 4.66 Point Elemental analysis 48.20 3.31 "4:54 48.33 4:06 4:42 ⁰ C Calculated 48.20 3.31 -5.11 45.26 3.14 4.96 204.5-206 51.21 3:52 "5:11 51.18 3.26 5:03 250 55.12 4.21 5:44 54.69 3:40 5.22 223.5-226 46.50 3:55 5.84 46.36 3.70 5:59 189-190 36.39 2:50 4.93 37.13 4:35 4.86 202-204 36.39 2:50 3.66 36.99 3:45 3.83 , 217-219 36.39 2:50 3.66 36.61 2.70 3.82 220-222 41.47 2.85 3.86 39.74 2.60 4:04 224-226.5 41.47 2.85 4:40 41.67 2.95 3.95 211-212 41.47 2.85 4:40 41.70 3.90 3.91 222-225 43.33 3:33 4:40 45.47 3.28 4.11 166-168 (dec.) 43.73 3:00 4.21 43.97 3.23 3.91 210-211 52.75 3.69 4.64 52.73 4:08 4.30 211-214 HHR (COCl ₃ ): 1.52 5.13 .74 (m.4H) 3:05 5:04 231-234 (P. H) ppm. (P.4HJ, 7.02-7 3.90 203.5-207 48.20 - 48.79 195-196.5 5.11 5.26 198-202 220-222.5

dec. = Decomposition

Example IX

Preparation of ethyl 1- (4-bromo-2-methylphenylaminocarbonyl) cyclobutanecarboxylate

Into a reaction flask purged with nitrogen was 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. With vigorous stirring, 2.80 g (0.01 mol) of ethyl 1-chlorocarbonylcyclobutanecarboxylate prepared in Example XIX was added 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. Rotary evaporation gave a crude product which was flash chromatographed over silica gel using 7: 3 hexane-ethyl acetate and 3.68 g (0.01 mol) of ethyl 1- (4-bromo-2-methylphenylaminocarbonylcyclobutanecarboxylate (Compound 129) as White solid recovered. A small sample was recrystallized from hexane and had a melting point of 61 ° C to 64 ^° C.

Example X

In the same manner as in Example IX, the compounds 130 to 134 which are listed in Table E below were prepared.

Table E Representative malonic acid derivative compounds

/ V

C CH

\ / R'O-C-C-C-NH

Connection Nr,

^C 2 ^H 5 ^C 2 ^H 5 C ₂ H ₅ ^C 2 ^H 5

substituents

Z '

3.5-Cl ₂ 2.4.5-Cl ₃

4-Cl

Elemental analysis N Found C H N .23 enamel Calculated 4:43 52.84 4.87 4 .94 Point C H 4:00 47.25 3.70 3 .11 V 53.18 4.78 4:43 52.84- 4.67 5 .92 76.5-80 47.95 4:02 4:43 53.14 4.71 5 __ 47-49 53.18 4.78 - - 59.89 5.70 011 53.18 4.78 011 59.68 5.73 85.5-87

Prepared by the mixed anhydride method according to Example XXXIII

-SG-

Example XI

Preparation of 1- (3, S-Di-chlorophenylaminocarbonylcyclobutanecarboxylic 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) and ethanolic potassium hydroxide (0.355 g , 0.006 mol) hydrolyzed. 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 (Compound 135) Formed a beige solid with a melting point of 159 ⁰ C to ^ .160 ⁰ C showed.

»

Example XII

In the same manner as in Example XI, compounds 136 to 139 were prepared, which are listed in Table F below.

Table F Representative malonic acid derivative compounds

HpC CH HO-C-C-C

Connection Nr,

136 137 138 139

substituents

2.4.5-Cl ₃

3.4-Cl 4-C1

C H N C Found N enamel 44.68 '50.02 50.02 S6.81 3.12 3.85 3.85 4.77 4.34 44.88 50.22 50.22 56.99 H 4.23 Point Elemental analysis 3.14 4.30 4.ΊΟ 4.94 ° C Calculated 146-147 129-132 151-153 159-161

Example XIII

Preparation of ethyl 1- (4-bromo-2-methylphenylatninocarbonyl) cyclopentanecarboxylate

Ethyl 1-chlorocarbonylcyclopentanecarboxylate (3.10 g, 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 (Compound 140) after recrystallization from hexane had a melting point of 64 C to 67 C.

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) were reacted under the same conditions as described in Example I to give 7.4 g (0.02 mol) of ethyl 2- (4-bromo-2-methylphenylaminocarbonyl) butanoate (Compound 141) as a white solid having a melting point of. 98 ° C to 100 ⁰ C.

Example XV

In the same manner as in Example XIV, compounds 142 to 152 shown in Table G below were prepared.

Table G Representative malonic acid derivative compounds

γ * γ ·

\ / ³

R'O is -C-C-C-NH

Ver C vs > ubs txtuent s vs ζ · ₇ C Elen N 3.72 alyse Found N 3.95 • 3.88 enamel My name is Nr _e vs 3 ^R> 5 S7.46 lentaran 4.20 H 4.11 3.86 Point 142 br H CH 2-CK -4-Br 75.66 Calculated 3:56 C 4.78 3.62 4.17 ⁰ C 143 br H ^C 2 ^H S 2.3- (CH-CHCH-CH) - 39.72 H 4.19 57.39 6:02 3.99 3:52 115-117 144 br ^CH 3 ^C 2 ^H S 2-CH ₃ -4-Br 43.07 4.82 - 75.60 3.68 4:41 115-117 145 br ^CH 3 vs 4-C1 39.05 5.74 3.80 40.13 4.29 B.74 Oil 146 br ^CH 3 vs 3,4-Cl 39.05 3.85 3.80 43.24 3.74 Oil 147 ^CH 3 ^CH 3 vs 2.4-C1 39.05 3.92 4.27 39.58 3:54 Oll 148 vs ^CH 3 ^C 2 ^H S 3.5-CI ₂ SI.23 3.28 3.93 39.56 3:53 OU 149 ^CH 3 vs 2-CH4-Br S3.94 3.28 4:46 39.80 P. 55 OTI ISO br vs 2-CH4-Or 49.10 3.28 8.62 51.49 ' 6:36 Oil is i H 2-CH4-flr 48.02 P. 53 53.89 p.18 OH : iS2 CM, 4-C * 6.23 49.51 4:53 117-11 · p.13 48.17 011 4:03

Oil = oil

- 1O0-

Example XVI

Preparation of 3- [(4-bromo-2-methylphenyl) 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 Water (0.06 g, 0.003 mol) and ethanolic potassium hydroxide (0.21 g, 0.003 mol) were hydrolyzed. 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 - [(4-8rom-2-methylphenyl) amino] -2-bromo-2-methyl-3-oxopropanoic acid (compound 153) as a white solid having a melting point of 133 C to 136 ⁰ C. -

Example XVII

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

A mixture of 4.90 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 moles) of N-butylamine, 150 ml of ethanol and 5 drops of water was stirred at room temperature for about 16 hours. After this period, the rotary evaporation gave a crude product in the form of a white solid. The white solid was recrystallized from ethyl acetate-hexane to give 3.08 g (0.009 mol) of N-butyl 3 - [(4-bromo-2-methylphenyl) amino -3-oxopropanaraid (Compound 154) having a melting point of 123 ⁰ C to 125 ^° C.

- 101 -

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. 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 extracted from the aqueous suspension with ethyl ether (4 × 400 ml). The ether extract was dried over magnesium sulfate, the solvent driven off in vacuo to give the monocarboxylic acid 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 slurry 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-chlorocarbonylcyclopropanecarboxylate (Compound 155). The NMR analysis of the product gave the following:

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

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

1 OiC ~ 4S.i # f «J i Ma

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 (CDCl ₃₎ 1.10 to 1.44 ft, 3H), 1.7 to 2.85 (m, 6H), 4.05 to 4.5 (q, 2H) ppm.

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 in 5.67 g (0.03 mol) of ethyl 1-chlorocarbonylcyclopentanecarboxylate (Compound 157). The NMR analysis of the product gave the following:

NMR _(CDCl3): 1.10 to 1.49 (t, 3H), 1.56 to 2.48 (m, 8H), 4.0-4.5 (q, 2H) ppm.

Example XXI Preparation of Ethyl 2-bromo-2-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-methyl malonate to 12.94 g (0.05 mol) of ethyl 2-bromo-2-chloro-carbonyl-propanoate (Compound 158). This connection was for

the preparation of compounds Nos. 144 to 148 and 152 used in Example XV. The NMR analysis of the product gave the following:

NMR _(CDCl3): 1.10 to 1.47 (t, 3H), 2.05-2.17 (s pair, 3H), 4.05 to 4.55 (q pair, 2H) ppm.

Example XXII

Preparation of ethyl 3-C (4-chlorophenyl) aminole-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, dour. Indian Chem. Soc. 45 (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 3,3-oxopropanoate (Compound 159) as white crystals with a melting point of 82 ⁰ C to 83 ⁰ C.

Example XXIII

Preparation of ethyl 3 - [(4-methylthiazol-2-yl) amino] -3-oxopropanoate

In the same manner as in the procedure described in Example I, 2-amino-4-methylthiazole was reacted with ethylmalonyl chloride using triethylamine as the acid acceptor in tetrahydrofuran solution. The product ethyl 3 - [(4-methylthiazol-2-yl) amino3-3-oxopropanoate (Compound 160) (7.5 g, 0.03 mol) was obtained as an off-white solid having a melting point of 138 ° C to 141 ⁰ C. won.

Example XXIV

In the same manner as in Example XXIII, compounds 161-173 listed in Table H below were prepared.

Table H Representative malonic acid derivative compounds

H ₅ C ₂ O

0 Il C - CH "- C - NH - R '

Il C

Connection no.

RV

Elemental analysis

Calculated

HN

Found

HN

melting point

Cl

[QT>

48.25 3.71 9.38 48.4fr 3.29 9.24 ISS-ISI

162

51.92 4.86 9.6S 58.08 4.63 9.62 164-168

163

164

Br CH ₃

'I

42.00 3.23 8.16 41.75 2.70 7.92 210 (dec.)

50.94 p. TO 13.20 p.13 p.69 13.11 63-65

dec. = with decomposition

Table H (Forts) Representative malonic acid derivative compounds

Connection no.

H ₁ -C ₀ O - C od.

RV

CH

CH ₃

O Il - CH ₀ -C-NH-R ¹

Elemental analysis

Calculated

HN

Found

melting point

HN

SO.94 p.70 "13.20 50.63 5.15 13.32 127-129

47.36 5.30 12.27 47.41 p.46 11.7t 90-92

32.78 3.09 9.N6 32.76 2.34 9. (2 US-US

U "

U9

44.43 p.36 17.27 44.13 p.41 17.41 148-1S0

49.SO 4.N7 11.54 49.30 4.51 11.54 65-68

encryption

Table H (cont.) Representative malonic acid derivative compounds

0 0 Il Il H ₅ C ₂ O - C - CH ₂ - C - NH - R * ₆

ν elemental analysis N C Found N enamel Calculated H Point C H ° C

"0 rV"^49S0 * ^{Λ1 η}·⁵<⁴⁹·³⁴ *^M  > »*« 99-100

16:24 132-13 *

Cl

S2.8S p. 76 6.16 S3.Ol p.81 6.11 011

CMj.

1J3(^ S WE (COCI₃):J1.11-1.4S(T.3H). 2.20 (1.3M). 2.36 (J.3H). 109-12 *

LU .. 3.46 (1.2H). 4.03-4.48 (q.2H). 6.6 (J.H). Ϊ.83 (t.H).

».06-i.Sl (br l.H> pp«.

VC / f '

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

Diethyl isopropylidene malonate (30 g, 0.15 mol) was saponified with 10.0 g (0.15 mol) 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 2-chlorocarbonyl-3-methyl-2-butenoate. NMR analysis of the residual product in CDCl 2 solution showed complete conversion of the carboxylic acid to the acid chloride, as evidenced by the absence of a subfield carboxylic acid proton.

This connection is referred to below as connection 174 ·

Example XXVI

Preparation of ethyl 2-C (4-bromo-2-methylphenyl) aminocarbonylH-3-methyl-2-butenoate

In the same manner as described in the procedure in Example I, ethyl 2-chlorocarbonyl-3-methyl-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) of ethyl 2 - [(4-bromo-2-methylphenyl) aminocarbonyl] -3- methyl-2-butenoate (compound 175) in the form of a white solid having a melting point of 116 ⁰ C to 119 ⁰ C.

Example XXVII Preparation of 3,4-dichloro-Z, 5-dimethylaniline

A solution of 5.0 g (0.03 mol) of 3,4-dichloro-2,5-dimethyl. 1-Nitrobenzene in 70 ml of ethanol was hydrogenated at room temperature and 50 psi in the presence of 0.25 g of 10% palladium on charcoal catalyst. The work-up of the reaction mixture gave 1.21 g (0.006 mol) of 3,4-dichloro-2,5-dimethylaniline (compound 176) as a yellow solid having a melting point of 72 ° C. to 76 ° C.

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

Part A: Preparation of 2,2-dimethyl-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) Mol) of trimethylacetyl chloride in a small amount of tetrahydrofuran solvent. The resulting mixture was stirred for two hours at room temperature. 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. This solution was washed with 2N HCL (2 ml) followed by water (1 x 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 recovered as a first and second crop. The NMR analysis of the product gave the following:

-709-

NMR (CDCl ₃ ): 1.32 (s, 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) propanatnide prepared in Part A in 150 ml of chloroform was added 3.81 g (0.03 mol) of sulfuryl chloride over a period of 40 minutes. The resulting mixture was refluxed for 3 days, with the mixture being cooled each day and an additional 3.81 g (0.03 mole) of sulfuryl chloride added before refluxing continued. After three 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-raethoxyphenyl) propanamic acid by flash column chromatography eluting with dichloromethane Obtained form of a bright yellow-orange solid. The NMR analysis of this product gave the following:

NMR (CDCl ₃ ): 1.34 (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-raethoxy-phenyl) -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 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-raethoxyaniline, as determined by thin layer chromatography. The above-mentioned dichloromethane fraction was

and gave a starting material, again refluxing with ethanol: 12N HCl overnight, working up and additionally providing 1.2 g (0.01 mol) of pure 4,5-dichloro-2-methoxyaniline as determined by thin layer chromatography has been. The NMR analysis of the product gave the following:>

NMR _(CDCl3): 8 3.88 (s, 5H), 6.73 to 6.90 (d, 2H) ppm.

Example XXIX

Preparation of 1- (4-bromo-2-methylphenylaminocarbonyl) cyclobutanecarboxylic 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 in the same manner as Example Xr "besenriemen g (0.007 mol) of 1- (4-bromo-2-methylphenylaminocarbonyl) cyclobutanecarboxylic acid Compound 181, having a melting point of 154 C to 155 C to recover.

Example XXX Preparation of ethyl (chlorocarbonyl) methoxyacetate Part A. Preparation of diethyl methoxymalonate

A mixture of 50.4 g (0.3 mol) of dimethyl methoxymalonate, para-toluenesulfonic acid (2.76 g) and 300 ml of ethanol was refluxed for about 24 hours. Subsequently, the volatiles were removed under reduced pressure using a 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. The removal of Etha

nol 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-ethylmethoxymalonate

A slurry 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 addition of potassium hydroxide. The solution was saturated with potassium chloride and extracted with methylene chloride (3 x 100 ml) to remove the unsaponified diester. Acidification to pH = 1 and continuous extraction with methylene chloride gave 9.45 g (0.06 mol) of mono-ethylmethoxymalonate 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 devolatilized. When the NMR investigation indicated that the reaction was not completed, the above-mentioned thionyl 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:

¹ H NMR (CDCl ₃₎ δ 1.16 to 1.53 (t, 3H, CH _3), 3.58 (s, 3H, CH ₃ O), 4.13 to 4.56 (q, 2H, CH ₂ ) 4.62 (s, H, CH) ppm.

- ΊΊ4.

Example XXXI

Preparation of ethyl 3-C (3, 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, with a melting point of 89.5 ° C to 92.5 ⁰ C to win.

Example XXXII Preparation of mono-methyl methoxymalonate

Dimethyl methoxymalonate (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. Work-up of the combined extracts gave 29.24 g (0.2 mol) of mono-methyl methoxymalonate , compound 214. The NMR analysis of the product indicated the following:

¹ H NMR (CDCl ₃ ) 5 3.54 (s, 3Η, 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-C (4-bromo-2-fluorophenyl) amino 3-2-methoxy-3-oxo-propanoate

To a stirred mixture of 2.78 g (0.02 mole) of mono-methylmethoxymalonate prepared in Example LVI (Compound 214) and 3.56 g (0.02 mole) of 4-bromo-2-fluoroaniline in approximately 100 mL of dry To tetrahydrofuran was added dropwise a solution of 3.87 g (0.02 mol) of 1,3-dicyclohexylcarbodiimide in about 30 ml of dry tetrahydrofuran while cooling the reaction mixture in an ice-water bath. The reaction mixture was then allowed to warm slowly to room temperature and stirring continued for a period of about 65 hours. The precipitated by-product 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 extracted with dilute HCl and then with water, then dried (MgSO ₄ ) and the solvent was evaporated in vacuo to give a colorless liquid, 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 volume of ethyl acetate gave 2.3 g (0.01 mol) of methyl 3 - [(4-bromo-2-fluorophenyl) araino] -2-methoxy-3-oxo-propanoate, Compound 215, with 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 Ha.

Table H a Representative malonic acid derivative compounds

OCH.

CH ₃ O -CCC-NH

Ver substituent 45.23 C elemental analysis C Found 3.91 enamel binding no. ² Ίο 49.49 - - Calculated 45.21 H 4.29 Point 216 3,4-Cl ₂ 43.73 HN 49.88 4:04 N ⁰ C 217 4-CF ₃ 40.46 3.45 4.80 43.73 3.22 4.20 78-81 218 4-Br 4.15 4.81 40.44 4.91 101-103 219 3.4.5-CI3 4:00 55-59 3.09. 117-121

Example XXXV

Preparation of t-butyl 3- [(3,5-dichlorophenyl) amino] -2-methoxy-3-oxopropanoate

Part A: Preparation of t-butyl methyl methoxymalonate

In a stirred solution of 9.26 g (0.06 mol) of methyl (chlorocarbonyl) methoxyacetate in 25 mL of carbon tetrachloride was added a mixture 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 in 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 100 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 (Mg _- SO.); 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-butylmethoxymalonate

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 5.43 g (0.03 mol) of mono-t-butyl methoxymalonate. The NMR analysis of the product gave the following:

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

Part C: Preparation of t-butyl 3-C (3,5-dichlorophenyl) aminol-2-methoxy-3-oxo-propanoate

Mono-t-butyl-araethoxy-salonate (5.42 g, 0.03 mol), 3,5-dichloroaniline (4.62 g, 0.03 mol) and 1,3-diol prepared in Part B. cyclohexylcarbondiiraid (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 - [(3,5-dichlorophenyl) aminole- 2-methoxy-3-oxopropanoate having a melting point of 129.5 ⁰ C to 131.5 ° C,

Example XXXVI

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

A mixture of 3.5 g (0.01 mol) of methyl 3 - [(3,5-dichlorophenyl) amino 3-2-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-disulfide and 35 ml of anhydrous 1,1-dimethoxyethane were stirred at room temperature for 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) -aminol-2-methoxy-3 Thioxopropanoat, compound 238, having a melting point of 144 C to 147 ⁰ C won.

Example XXXVII

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

Part A: Preparation of diethyl bis (2,3-trimethylsilyl) cyclopropene-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 ° C. 39.3 g (0.21 mol) of diethyldiazomalonate were added over a period of 36 hours by means of a syringe pump. After all of the diazomalonate had been added, was heated for another 12 hours at 145 ⁰ C. The excess bis (trimethylsilyl) 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-dicarbonylate as a yellow liquid. The NMR analysis of the product gave the following:

¹ H NMR (CDCl ₃ : δ 0.23 (s, 18H), 1.20 (t, 6H), 4.17 (q, 4H) ppm.

Part B: Preparation of diethylcyclopropene-1-dicarboxylate

A 500 ml round bottom flask was equipped with magnetic stir bar and N ₂ 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, Filled 50 g (0.02 mol) dicyclohexano-lS-crown-ö-ether. The mixture was stirred for 6 hours at room temperature. The mixture was filtered and the filtrate concentrated under reduced pressure to a deep red oil.

- 11 f-

This oil was taken up in 100 ml of methanol and stirred at room temperature for 24 hours. 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-dicarboxylate as a yellow oil. The NMR analysis of the product gave the following:

¹ H NMR _(CDCl3): δ 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 N ₂ inlet funnel. The flask was charged with 6.15 g (0.03 mol) of diethylcyclopropene 1,1-dicarboxylate and 50 ml of ethanol. The stirred. The 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 10% HCl and extracted three times with ethyl acetate. The ethyl acetate was dried (MgSO ₄ ) and the solvent was removed under reduced pressure leaving an orange solid. This was recrystallized from hexane-ethyl acetate to give 3.65 g (0.02 mole) of mono-Ethylcyclopropen-1,1-dicarboxylate as a light yellow solid having a melting point of 76.0 ⁰ C to 77.5 C. The NMR Analysis of the product revealed the following:

¹ H NMR (CDCl ₃ ): 6 1.20 (t, 3H), 4.25 (q, 2H), 6.80 (s, 2H), 11.5 (br s, IH) ppm.

Part D: Preparation of 1-Carboethoxy-1-ethoxycarbonyloxycarbony1-2-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-dicarbonylate, 50 ml of dry THF, 2.3 g (0.02 mol) of potassium carbonate (anhydrous) and 450 mg of dicyclohexano-18-crown. 6 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 point, an aliquot of the reaction mixture at 1820 cm in the infrared showed a very strong anhydride carbonyl stretch, suggesting the formation of mixed anhydride 1-carboethoxy-1-ethoxycarbonyloxycarbonyl. 2-cyclopropen hinwies. The remainder of the reaction mixture containing the mixed anhydride was further used in Part E.

Part E; Preparation of 2-cyclopropenyl-1-carboethoxy-1- [N- (2-methyl-4-bromophenyl) -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 to yield an orange solid. 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- [N- (2-methyl-4-bromophenyl) -carboxamide, Compound 256, recovered in the form of a white crystalline solid having a melting point of 151 ⁰ C to 153 ⁰ C.

Example XXXVIII

Effect of Representative Malonic Acid Derivative Compounds on Yield Increase - Leaf-axel Stimulation in Plants

The axillary stimulation may be an indication of more plant reproductive sites leading to higher biomass and / or higher crop yield. Treatment of the plants with certain malonic acid derivative compounds, such as the compounds listed in Table I below, results in enhanced axillary stimulation. Solutions of the test compounds listed in Table I were prepared by dissolving 68.8 mg of the appropriate compound in 5.5 ml of acetone and then adding water to a final volume of 11.0 ml. If turbidity of the solution occurred on addition of water, the use of water was discontinued and acetone was 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 concentrations in parts of the test compound per million parts by weight of the final solution used in the foliar pelvic stimulation tests of Table I were obtained by suitable dilution of the stock suspensions with water and acetone (50/50 volume / volume). Seeds of green beans, wheat, woolly honeygrass, cucumber, sunflower, flax, buckwheat, tomato, hardy rye, calendula, soybeans, millet, wild oats and peas were grown in sandy loam soil in a dish with the following dimensions: 3.5 inches wide χ 7.9 inches in length χ 1.0 inches in height. At 12 to 14 days post-plugging, by the time the first green bean trifoliolate leaf was at least 3.0 cm long, each concentration of the test compounds listed in Table I was adjusted as a foliar spray by means of an air pressure set to 10 psig Aspirator sprayer (all dishes were given at 4 pounds

per acre splashed). As a control, a water-acetone solution containing no test compound was also sprayed on a dish. After drying, all the plant shells were placed in a greenhouse at a temperature of 80 ⁰ F + _ 5 ° F and a humidity of 50 % + _ 5 % . Ten to fourteen days after treatment, visual signs of the effectiveness of leaf axillary irrigation were observed and recorded. Visual observations of axillary stimulation were recorded using a numerical rating system. The numerical scores from "0" to "10" were used to indicate the degree of effectiveness of the leaf-axel stimulation observed in comparison to the untreated control. A rating of "0" shows no visible response, a rating of "5" indicates 50 % higher leaf-axel stimulation than the control, and a "10" indicates 100 % higher leaf-axel stimulation than the control. This evaluation system shows the degree of bud growth from the leaf axils on broadleaf plants and the degree of tillering of grasses compared to an untreated control group

 The results are listed in Table I.

- 1ZZ-

, Table I

Effect of Representative Malonic Acid Derivative Compounds on Increasing Yield - Leaf Frizz Stimulation

green beans

Connection No. Valuation of Leaves,

achseistimulierung

Control 0

1 - ₍ 1

2 2

3 1 5 1 8 1

j 9 1

11 1

15 1

21 1

22 5

23 2

24 2

25 1

26 3

27 1

28 1

34 5

35 1

36 - 1

37 1

38 1 40 1 43 1

46 3

47 1 50 1

57 1

58 1,

Table I (cont.)

Effect of Representative Malonic Acid Derivative Compounds on Increasing Yield - Leaf Frizz Stimulation

green beans

Connection no. Review of the sheet Axis! Stimulation 66 1 67 2 68   .2. 69 2 70 2 71 1 75 6 79 1 80 1 82 1 83 1 84 1 86 1 88 1 90 1 92 1 95 1 98 1 99 1 100 1 101 1 102 2 105 1 107 1 108 1 110 2 111 2 112 1 114 2

Table I (cont.)

Effect of Representative Malonic Acid Derivative Compounds on Yield Increase - Leaf-axel Stimulation

green beans

Connection no. Review of the sheet axillary stimulation 115 1 116 1 117 1 120 1 • 121 1 122 1 123 1 125 2 126 2 129 1. 135 1 140 1 141 2 144 2 145 1 146 1 148 2 149 1 150 1 159 2 168 · 1 173 1 175 4

Table I

Effect of Representative Malonic Acid Derivative Compounds on Yield Increase - Foliar Stimulation

wheat

Connection no. ft > Evaluation of the sheets Control ·. oh seismic simulation 1 2 O 14 2 22 1 66 2 67 1 69 3 88 3 96 1 97 1 83 4 175 3 144 2 129 1 116 1 117 i 121 1 146 1 145 1 1 1

The results in Table I show that treatment of the plants with certain malonic acid derivative compounds allows significantly enhanced axillary stimulation, indicating more plant reproductive sites, resulting in higher plant biomass and / or higher crop yield.

Example XXXIX

Effect of Representative Malonic Acid Derivative Compounds on Yield Increase - Wheat .

Solutions of compound 75 were prepared by adding 0.48 g each. 0.96 g or 1.92 g of the compound were dissolved in 800 ml of acetone. Water plus 0.2% by volume of spraying aid Surffeik was added to each of the above solutions to a final volume of 1600 ml.

The above formulations were applied to wheat using a statistical treatment method on 42 separate lots. The plot consisted of 8 rows of 30 feet each and about 0.75 feet between rows. The entire plot was treated with the solutions listed in the following Table Cl containing the active ingredient. The experiment was designed as a random complete block of six different repetition experiments »each repetition involving:

1) an untreated control;

2) treatment with 0 ^ 48 g / plot of compound 75 at time T, reported in Table 3;

3) Treatment at 0.96 g / plot of Compound 75 at time T ₁ , shown in Table Ji

4) treatment at 1.92 g / plot of Compound 75 at time T, reported in Table 3;

5) Treatment with 0 ^ 48 g / lot of compound 75 at time T ₂ reported in Table 3;

5) Treatment at 0.96 g / plot of Compound 75 at time T ₂ reported in Table D; such as

7) Treatment at 1.92 g / plot of Compound 75 at time T ₂ * reported in Table 3.

The above formulations were applied to each plot using a carbon dioxide backflush sprayer at about 30 psig air pressure. The sowing, application and harvest times for each crop are detailed in Table D. The yield yielded wheat crops were from the inner 20 feet of the middle 4 rows in each plot (starting 5 feet from the respective ends of the four middle rows). The values obtained on each plot at each repetition were averaged to obtain the results of Table 3. "

Two weeks prior to harvest, samples (sub-samples) of the wheat plants were taken from 2 separate 1 square foot sections of each plot and the numbers of inflorescences and seeds per inflorescence were determined. The values from the sub-samples per plot were averaged together with the values obtained from each plot at each repetition to obtain the results in Table D.

Table D

Effect of Representative Malonic Acid Derivative Compounds on Yield Increase - Wheat

Time d,

Connection no. Concentration (g / plot) control - Connection 75 0.48 0.96 1.92 Connection 75 0.48 0.96 1.92

Inflorescence per square foot Seeds per inflorescence Actual yield (kg / parcel) 66 29 4.9 72 29 5.3 64 30 5.0 64 31 5.0 67 28 5.0 64 29 5.0 66 28 5.0.

a ) 'The first application was made after the appearance of the flag leaf (T ₁ )

\ 49 days after sowing; the second application was made at the full development of the flag leaf (T ₂ ), 53 days after sowing, and the harvest was made 79 days after sowing.

The results in Table 3 demonstrate that the treatment of wheat with certain malonic acid derivative compounds brings significantly increased yields compared to untreated control wheat. As can be seen from Table Cl, the higher yield can be attributed to a greater number of inflorescences or a greater number of seeds per inflorescence or a combination of both.

, Example XL

Effect of Representative Malonic Acid Derivative Compounds on Increasing Yield - Alfalfa

Solutions of Compound 75 were prepared by dissolving 70 mg, 140 mg or 280 mg each of the compound in 87 ml of acetone. Water plus 0.2% by volume of Triton X-100 surfactant was added to each of the above solutions to a final volume of 174 ml.

The above formulations were applied to alfalfa by a statistical treatment method with 24 separate plots. Each plot was 5 feet by 10 feet tall. The entire plot was treated with the solutions listed in the following Table K. containing the active ingredient. The experiment was designed as a random complete block of six different repetition experiments, each repetition involving:

1) an untreated control;

2) Treatment with 70 mg per plot of Compound 75 45 days after planting;

3) Treatment with 140 mg per lot of compound 75 45 days after planting; and

4) Treatment with 280 mg per plot of Compound 75 45 days after planting.

The above formulations were applied by means of a mobile carbon dioxide sprayer with an air pressure of about 30 psig. Three weeks after treatment, eight plants per plot were harvested. The plants were divided into stems and leaves, placed in a drying oven and dried for 48 hours at a temperature of 90 Ό. The leaf and stem parts were weighed separately and the values are listed in Table K. The total dry weight and leaf / stem ratio were calculated from the leaf and stem dry matter values and the results are listed in Table K. The values from each plot in each repeat experiment were averaged to obtain the results listed in Table K below.

Table K the Ert ragssteigerung - Lucerne Total dry mass (9) Ratio of leaf / stem % Increase in leaf / stem ratio Sheet dry mass (9) Stem dry mass (9) 3.91 4.28 4.63 4.60 1.54 1.83 2.09 2.34 19 36 ι 52 2.37 2.76 3.12 3.20 1.55 1.51 1.51 1.40 Connection no. Effect of representative malonic acid derivative compounds Control connection 75 on Concentration (g / plot) 0.7 1.4 2.8

The results in Table K demonstrate that the treatment of alfalfa with certain malonic acid derivative compounds brings significantly higher yields compared to untreated control glucoses. As shown in Table K, the treated alfalfa had higher leaf dry mass, reduced dry stone mass and higher total dry mass (leaves and stems) as compared to the untreated Kontro lucerne. A significant increase in leaf / stem ratio in treated alfalfa as opposed to untreated control alfalfa is demonstrated by the results in Table K.

Example 'XLI ~

Effect of Representative Malonic Acid Derivative Compounds on Increasing Yield - Soybeans

Solutions of Compound 75 were prepared by dissolving 0.39 g each, 0.78 g, or 1.56 g of the compound in 650 mL of acetone. Water plus 0.2% by volume of the spray additive Surfelk was added to each of the above solutions to a final volume of 1300 ml.

The above formulations were applied using a random treatment procedure with 42 separate plots. Each parcel consisted of 4 rows of 20 feet each and about 3 feet between rows. The two middle rows of each plot were treated with the solutions listed in Table L below containing the active ingredient. The experiment was designed as a random complete block of six different repetition experiments, each repetition involving:

1) an untreated control;

2) Treatment at 0.39 g / plot of Compound 75 at time T ₁ reported in Table Lj

3) treatment at 0.78 g / plot of Compound 75 at time T ₁ reported in Table L;

4) Treatment with 1.56. g / lot of compound 75 at time T ₁ reported in Table L;

5) Treatment with 0.39 g / plot of Compound 75 at time T ₂ reported in Table Lj

6) Treatment with 0.78 g / plot of Compound 75 at time T ₂ * reported in Table Lj and

7) Treatment with 1.56 g / plot of Compound 75 at time T ₂ reported in Table L.

The above formulations were applied to each plot with the aid of a carbon dioxide backflush sprayer at about 30 psig air pressure. The plug ,. Application and harvest times are listed in Table L. The soybean plants harvested for yield were from the inner 10 feet of the two middle rows of each plot (starting 5 feet from the respective end of the two middle rows). The values (kg soybean / plot) from each repeat experiment obtained on each plot were averaged to obtain the To obtain results in Table L.

Four weeks after application at time T ₂ , eight soybean plants were sampled from each plot to determine the number of fruits (pods) per plant. The values obtained from each plant were averaged to obtain the results in Table L.

Table L

Effect of Representative Malonic Acid Derivative Compounds on Increasing Yield - Soybeans

Connection no.

Concentration application (g / plot) Time ⁸

Control connection 75

Connection 75

0.39 0.78 1.56

0.39 0.78 1.56

Flowering time (T ₁ ) Flowering time (T ₁ ) Flowering time (T ₁ )

3 weeks after flowering (T ₂ ) 3 weeks after flowering (T ₂ ) 3 weeks after flowering (T ₂ )

Pods per plant Actual yield (kg / parcel) 74 1.17 77 1.21 91 1.58 81 1.37 102 1.84 175 1.47 122 1.13

First application at flowering time (T ₁ ), 77 days after plugging; second application 3 weeks after flowering period (T _2), 98 days after the plugging and harvest after 180 days after plugging "

The results in Table L show that the treatment of soybean plants with certain malonic acid derivative compounds in certain amounts yields significantly higher yields compared to untreated control soybean plants. As shown in Table L, in addition to an actually higher yield (kg soybean / plot), the treated soybean plants had a greater number of pods per plant as compared to the untreated control soybean plants.

Example XLII

Effect of Representative Malonic Acid Derivative Compounds on Increasing Yield - Soybeans

Solutions of Compound 75 were prepared by dissolving 0.75 g or 1.5 g each of the compound in 125 mL of acetone. To each of these solutions was added water to a final volume of 250 ml.

The above formulations were applied to soybean plants using a statistical procedure with 36 separate lots. Oede plot consisted of 4 rows of 25 feet each with a gap of 2.5 feet between rows. The two middle rows of each plot were treated with the solutions listed in the following Table M containing the active ingredient. The experiment was designed for split plots with six different repetitions. The experiment was divided into two blocks as follows: Block 1 consisted of the plots treated at the time of the first flowering and block consisted of the plots treated 3 weeks after the first flowering. Coincidentally, in each block were arranged:

1) an untreated control;

2) Treatment with 0.75 g of Compound 75; and

3) Treatment with 1.5 g of Compound 75.

The above formulations were applied to each plot with the aid of a carbon dioxide backflush sprayer at about 30 psig air pressure. The insertion, application and harvest times are listed in Table M. The two middle rows of each plot were harvested to determine the yield. The values obtained from each plot in each repetition were averaged to obtain the results in Table M.

Four soybean plants were randomly harvested from each plot to determine the number of fruits (pods) per plant four weeks before the harvest. The values obtained from each plant were averaged to obtain the results of Table M.

Table M

Effect of Representative Malonic Acid Derivative Compounds on Increasing Yield - Soybeans

Connection no.

Concentration application (g / plot) Time ⁸

control 75 __ connection 0.75 1.50 control 75 __ connection 0.75 1.50

first flowering (T ₁ )

first flower (T ₁ ) first flower (T.)

3 weeks after the first flowering (T ₂ )

3 weeks after the first flowering (T ₂ ) 3 weeks after the first flowering (T ₂ )

a ) Application at the first flowering time (T ^), 52 days after insertion, · Application 3 weeks after the first flowering period (T ₂ ), 73 days after insertion and harvest 167 days after insertion.

Pods per plant Actual yield (kg / parcel) 59 3.74 70 4.17 73 3.94 69 3.58 75 3.56 61 3.78

- -TSf-

The results in Table M demonstrate that the treatment of soybean plants with certain malonic acid derivative compounds in specific amounts yields significantly higher yields compared to untreated control soybean plants. As shown in Table M, the treated soybean plants had a higher number of pods per plant compared to the untreated control soybean plants in addition to a higher actual yield (kg soybean / plot).

Example XLIII

Effect of Representative Malonic Acid Derivative Compounds on Increasing Yield - Green Beans

Solutions of Compound 75 were prepared by dissolving 1.56 mg, 3.13 mg, or 6.25 mg each of the compound in 5 ml of acetone and then adding water to a final volume of 10 ml.

In plastic pots with a diameter of 10.2 cm, which contained a pot mix of perlite / vermiculite (1: 2 volume / volume), three bean seeds ( Phaseolus vulgaris var, cranberry) were sown. Five to seven days later, the plants were singulated to one plant per pot. Ten to twelve days after sowing, at the time the primary leaves were fully deployed, each concentration of Compound 75 (each pot was sprayed with 1 ml of solution) was applied as a foliar spray to 10 bean plants using an aspirator sprayer with a 10 psig air pressure. Untreated plants were run as controls. After drying, all plants were placed in a climate chamber Sherer model FAL22R with day / night temperatures of 80 ° F / 65 ⁰ F and a 15-hour light time per day. 67 days after sowing, the plants were removed from the climatic chamber, harvested and the total number of fruits (pods) per plant was determined. The one from each

- $ 13 -

Plant values were averaged and gave the results in Table N below.

table N - Green beans Wirkunq of Number of (pods) r fruits per plant on Representative Malonsäurederivatverbindunqen 34 44 45 44 Connection no. the increase in yield Control connection Concentration (ppm) 75 156 313 625

The results in Table N demonstrate that the treatment of bean plants with certain malonic acid derivative compounds gives significantly higher yields compared to untreated control bean plants. A significant increase in the number of fruits (pods) per treated bean plant as opposed to untreated control bean plants is shown by the results in Table N.

Example XLIV

Effect of Representative Malonic Acid Derivative Compounds on the Chlorophyll Content of Plants

An elevated chlorophyll content may be indicative of greater photosynthetic activity due to increased biomass and / or higher crop yield. Treatment of the plants with certain malonic acid derivative compounds, such as compound 75, and as described below, results in higher chlorophyll levels.

Solutions of compound 75 were prepared by dissolving 1.56 mg, 6.25 mg, or 25.0 mg each of the compound in 5 mL of acetone and then adding water to a final volume of 10 mL.

In plastic pots with a diameter of 10.2 cm, which contained a pot mix of perlite / vermiculite (1: 2 volume / volume), three bean seeds ( Phaseolus vulqaris var. Cranberry) were sown. Five to seven days later, the plants were singulated on a plant per pot. Eleven days after seeding, at the time the primary leaves were fully deployed, each concentration of compound 75 (each well was sprayed with 1 ml of solution) was applied as a foliar spray to 10 bean plants using an aspirator set at 10 psig. Untreated plants were run as controls. After drying all plants were placed in a greenhouse with a temperature of 80 ⁰ F + 5 ⁰ F and a humidity of 50 % _ + 5 % . 11 days after treatment, 15 slices (10 mm in diameter) were punched from the primary leaves of each plant. The set of 15 slices were weighed, placed in a test tube and stored in the dark on ice. Each set of slices was then homogenized in a Waring blender with 20 ml of a solution containing 80 % acetone and 20 % water (volume / volume). The obtained suspensions were at a temperature of 0 ⁰ C to 2 ⁰ C at

-2

12000 g (g = 980 cm s) centrifuged for 5 minutes.

The supernatant containing the chlorophyll was stored and the absorbance of the light of the solutions at 645 nanometers (nm) and 663 nanometers (nm) was determined by spectrophotometry. All chlorophyll (milligrams chlorophyll / gram leaf tissue) was calculated according to the following formula:

(20.2) (absorbance at 645 nra) + mg chlorophyll (8.02) (absorbance at 663 nm)

g leaf tissue mass of leaf discs (g)

The values obtained from the control and Compound 75 were averaged and provided the results of Table 0 below.

Table 0

Effect of Representative Malonic Acid Derivative Compounds on the Chlorophyll Content of Plants

Compound Concentration Chlorophyll content No. (PP ^m ) ( ^m g chlorophyll / g leaf

tissue)

Control - 60.1

Compound 75 156 72.6

625 78.7

2500 82.1

The results in Table 0 demonstrate that the treatment of plants with certain malonic acid derivative compounds brings significantly higher levels of plant chlorophyll compared to untreated control plants. This increase in Pflanzenchlorophyllgehaltes may indicate the larger plant biomass and / or on the increase in yield.

Example XLV

Effect of representative malonic acid derivative compounds on the nitrate reductase content of the plant

Nitrate reductase is a substrate-inducible enzyme that is a linker for the conversion of nitrate to nitrite. The inducible nature of nitrate reductase and the dependence of enzyme content on substrate content provides the plant with a controlled growth mechanism. Nitrate reductase catalyzes the rate-limiting step in the conversion of nitrate into proteins. Thus, the elevated levels of nitrate reductase may be an indication of the increased potential for grain and protein production. See, for example, Beevers, L. and R.H. Hageman, 1969, Nitrate Reduction in Higher Plants, Annual Review of Plant Physiology 20: 495-522.

Solutions of Compound 75 were prepared by dissolving 1.56 mg, 6.25 mg, or 25.0 mg each of the compound in 5 mL of acetone and then adding water to a final volume of 10 mL.

In plastic pots with a diameter of 10.2 cm, which contained a pot mix of perlite / vermiculite (1: 2 volume / volume), three green beans ( Phaseolus vulgaris var. Cranberry) were inserted. Five to seven days after plugging, the plants were singulated to one plant per pot. Eleven days after plugging, at the time the primary leaves were fully deployed, each concentration of Compound 75 (each pot was sprayed with 1 ml of the solution) was applied as a foliar spray to 10 bean plants using an aspirator set at Iq psig barometric pressure. Untreated plants were run as controls. After drying, all plants were placed in a greenhouse with a temperature of 80 ⁰ F + 5 ⁰ F and a humidity of 50 % + _ 5%.

Seven days after treatment, groups of 5 slices (each 1 era in diameter) were randomly excised from the primary leaves. The slices were weighed, then infiltrated under vacuum for 3 minutes in 3 O ral beakers containing 10 ml of a given medium. The medium consisted of O _f .l hä phosphate buffer (pH 7.5), 0, CS M potassium nitrate and 0.1 % (v / v) Triton X-100.

The cups were then covered and stored for 90 minutes at a temperature of 32 ⁰ C in the Brutkamraer. At the beginning of the incubation period, as well as after 20 minutes and 80 minutes during the incubation period, the nitrate released into the medium was detected by taking an aliquot of 0.2 ral from each beaker and placing it in a test tube. In the test tube was added 0.25 ml of 1% (mass / volume) sulfanilamide in 3NHCl and 0.25 ml of Q, Q 2% (mass / volume) N- (1-naphthyl) ethylenediamine dihydrochloride. The test tubes were then allowed to stand for 20 minutes before measuring the optical density at 540 nm on a Beckman DB spectrophotometer. The nitrate reductase activity was expressed as micromoles (M) of nitrites formed per gram of fresh leaf mass per hour. The values obtained from the control and Compound 75 were averaged to obtain the results of Table P below.

- -ryy-

Table P Nitratreductase content of the plant Nitrate reductase activity (micromoles N0 ₂ - / gram / hour) Wirkunq of Concentration (ppm). 1, 6, 4, 4, on 156 625 2500 , 81, 56, 71, 06 Connection no. Representative Malonsäurederivatverbindunaen Control connection the 75

The results in Table P demonstrate that treatment with certain malonic acid derivative compounds brings significantly higher levels of nitrate reductase compared to the untreated control plants. This increased nitrate reductase content of the plant may be an indication of increased plant protein production and / or increased yield performance.

Example XLVI

Effect of representative malonic acid derivative compounds on the increase in yield - tillering of wheat

Solutions of the test compounds listed in Table Q below were prepared by dissolving the compounds in acetone / water (50:50 v / v) containing the 0.05 % volume / volume Triton X-100 surfactant. As will be described in detail below, these solutions of the test compounds were applied to wheat in a concentration of 0 _f 06, 0.12, 0 _f 25, 0.50 and l, respectively. _R o pounds of active ingredient per acre applied.

- 1HS-

Wheat seed (Olaf variety) was planted in sandy loam soil in shells of the following diameter: 5.5 inches wide χ 9.0 inches long χ 3.0 inches high. The wheat grains were sown in 2 different distributions: 4 rows (5 inches long) per tray, 10 seeds per row (tray "# 1), and 2 rows (5 inches long) per tray, 5 seeds per row (" Shell No. 2) Eleven days after sowing, at the time of the 2-3 leaf stage of wheat, each concentration of the test compounds listed in Table Q was applied to each individual shell using a 10 psig air pressure aspirator sprayer (each all trays were sprayed at a concentration of 120 gallons per acre.) As a control, a water-acetone solution containing no test compound was also sprayed on separate trays After drying, all trays were transferred to a greenhouse with a temperature of 80F + _ 5 F and a humidity of 50 % + _ 5 % 15 days after the treatment was sown on the wheat after the arrangement in shell no the degree of tillering was observed and recorded, and the same was done 20 days after the treatment on the wheat seeded after being placed in dish # 2.

The number of vegetative lateral shoots per seed was determined by counting. The results listed in Table Q reflect the mean of 3 repetitions. The percentage increase in tillering refers to the untreated control plants.

Table Q

Effect of Representative Malonic Acid Derivative Compounds on the Yield Increase - Stocking of Wheat

Connection No. ₀ Quantity (pounds per acre) Tillering (side shoot / seed) Percentage increase in tillering Control* 2.0 0 75 * 0.06 2.5 25 0.12 2.7 35 0.25 2.6 30 0.50 3.5 75 111 * 0.06 4.8 140 • 0.12 5.5 175 0.25 5.7 185 0.50 6.1 205 Control** - 6.5 0 75 ** 0.25 6.6 2 0.50 7.8 20 1.0 8.6 32 111 ** 0,015 9.9 52 0,030 12.1 86 0,060 13.8 112

Arrangement shell No. 1 Arrangement shell No. 2

The results in Table Q demonstrate that the treatment of wheat with certain malonic acid derivative compounds results in significantly higher tillering compared to untreated control wheat.

Claims (32)

claims f. A method of increasing the yield, .gege characterized by the fact that an increase in yield sufficient effective amount of a compound of the following formula is applied to the crop: ^Y 3 R ,. - Y ,, - C I ^Y 5 ' ^Y 6 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 in which the permissible substituents (Z) are identical or different and are one or more of hydrogen, halogen, alkylcarbonyl, alkylcarbonylalkyl, formyl, alkoxycarbonylalkyl, alkoxycarbonylalkylthio, polyhalogenoalkenylthio, thiocyano, propargylthio, hydroxyimino, alkoxyimino, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, Formamidino, alkylsulfamido, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfonyl, hydroxy, amino, azido, azo, aminocarbonyl, alkylaminocarbonyl, hydrazino, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothi ocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formamido, alkyl, alkoxy, polyhaloalkyl, polyhaloalkoxy, alkoxycarbonyl, substituted amino, wherein the permissible substituents - 2 - 257 57 are the same or different and are one or two of propargyl, alkoxyalkyl, alkylthioalkyl, alkyl, alkenyl, haloalkenyl or polyhaloalkenyl; Alkylthio, polyhaloalkylthio, alkylsulfinyl, polyhaloalkylsulfinyl, alkylsulfonyl, polyhaloalkylsulfonyl, alkylsulfonylamino, alkylcarbonylaraino, polyhaloalkylsulfonylamino, polyhaloalkylcarbonylamino, trialkylsilyl, aryldialkylsilyl, triarylsilyl, sulfonic acid and derivative salts, phosphonic acid and derivative salts, alkoxycarbonylamino, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkenyl, polytialo. genalkenyl, alkenyloxy, alkynyl, alkynyloxy, polyhaloalkenyloxy, 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, arylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, haloalkenyloxy, haloalkynyloxy, haloalkynylthio, haloalkenylsulfonyl, polyhaloalkenylsulfonyl, isocyano, aryloxysulfonyl, propargyloxy, aroyl, haloacyl, Polyhaloacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, carboxyalkoxy, carboxyalkylthio, alkoxycarbonylalkoxy, acyloxy, haloacyloxy, pol yhalogenacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhalogenoalkylsulfonyloxy , aroylamino , haloacylamino, alkoxycarbonyloxy, arylsulfonylamino, aminocarbonyloxy, cyanato, isocyanato, isothiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl (alkyl) amino, aralkylamino, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, Alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamines, alkoxyamino, aryloxyamino, aryloxyimino, oxo, thiono, Diazo, alkylidene, alkylimino, hydrazones, semicarbazono, dialkylsulfonium, dialkylsulfuranylidene, dialkyloxosulfuranylidene, -X, = X, -X ⁼ X ^- R ^- ,, Y_ _X _ R ₃ , - ρ - Y ₈ R ₄ or ^Y 8 ^R 4 " ^Y ' ^Y 8 ^R 4 ^Y 9 ^R 5 ; or R ₁ 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 wherein the permissible substituents are Z; Y ₁ and Y ₂ are independently a substituted or unsubstituted heteroatom wherein the permissible substituents are; ', Y ₃ and Y. are independently hydrogen or 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 or halogen, alkylcarbonyl, formyl, alkylcarbonylalkyl, alkoxycarbonylalkyl , Alkoxycarbonylalkylthio, polyhaloalkenylthio, thiocyano, propargylthio, trialkylsilyloxy, aryldialkylsilyloxy, triarylsilyloxy, formamidino, alkylsulfamide, dialkylsulfamido, alkoxysulfonyl, polyhaloalkoxysulfony1, hydroxy, amino, hydrazino, azo, aminocarbonyl, alkylaminocarbonyl, Azido, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, nitro, cyano, hydroxycarbonyl and derivative salts, formarnido, 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, 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, Halogenalkynyloxy, HaIogenalkynylthio, haloalkenylsulfonyl, Polyhalogenalkenylsulfonyl, isocyano, aryloxysulphonyl, propargyloxy, aroyl, haloacyl, Polyhalogenacyl, aryloxycarbonyl, aminosulfonyl, alkylaminosulfonyl, Dialkylam "nosulfonyl, arylaminosulfonyl, carboxyalkoxy, Carboxyal'ylthio, alkoxycarbonylalkoxy, acyloxy, Haloacyloxy, polyhalogenacyloxy, aroyloxy, alkylsulfonyloxy, alkenylsulfonyloxy, arylsulfonyloxy, haloalkylsulfonyloxy, polyhaloalkylsulfonyloxy, aroylamino, haloacylamino, alkoxycarbonyloxy, arylsulfonylaraino, aminocarbonyloxy, cyanato, isocyanato, iso thiocyano, cycloalkylamino, trialkylammonium, arylamino, aryl (alkyl) amino, aralkylamines, alkoxyalkylphosphinyl, alkoxyalkylphosphinothioyl, alkylhydroxyphosphinyl, dialkoxyphosphino, hydroxyamino, alkoxyamino, aryloxyamino, -X, -X = ^ 3 ' Y ₇ Y ₇ I! Il -X - R ₃ , - P - Y ₈ R ₄ , -Y ₁₀ - P- Y ₈ R ₄ wherein the permissible substituents are Z; or Y ₃ and Y. taken together are oxo, thiono, diazo, = X or = XR, or substituted or unsubstituted alkylidene, alkylimino, hydrazono, dialkylsulfonium, dialkylsulphanylidene, dialkyloxosulphanylidene, semicarbazono, dialkylsulphonium, dialkylsulphanylidene, dialkyloxosulphanylidene, hydroxyimino, alkoxyimino or aryloxyimino, wherein the permissible substituents are Z; or Y- and Y. 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, wherein the permissible substituents are; and Y ₅ and Y _β are independently oxygen or sulfur; in which 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- 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; or R-z 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 are Z; Y ₇ and Yq are independently oxygen or sulfur; Yo and Yg are independently oxygen, sulfur, amino or a single covalent bond; and R. and R ₅ are independently hydrogen or substituted or unsubstituted alkyl, alkenyl, alkynyl, polyhaloalkyl, phenyl or benzyl, wherein the permissible substituents are Z; A method according to claim 1, characterized in that the compound has the formula: "· 7" 257 57 in which represent: R ₁ , Ro " ^γ -) ' ^Y 2' ^Y 5 * ^Υ 6 ^{and Ζ have the} meaning set ^{forth in} claim 1 and Y ₃ and Y _{4 taken} together are oxo, thiono, diazo, = X or = XR ,, or substituted or unsubstituted alkylidene, alkylimino, hydrazono, dialkylsulfonium, dialkyloxosulfoniurea, semicarbazono, dialkylsulfonium, dialkyloxosulfonium, hydroxyimino, alkoxyimino or aryloxyimino, wherein the permissible substituents are Z. A process according to claim 1, characterized in that the compound has the formula: wherein: Ri R ₂ ' ^Y i' ^Y 2 ^JY 5 ' ^Y 6 ^unc ' ^z have the meaning explained ⁱⁿ claim 1 and Y ₃ and Y ₄ are linked together and 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 may be saturated or unsaturated, wherein the permissible substituents are Z. ^ T. The method of claim 1, ge Ind eichnet characterized in that the compound has the following formula: 0 0 Z'g R ' ₇ - Y'33 - C - CH ₂ - C - NH - J' in which represent: Z'g is the same or different and 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 ^f ₃₈ is O, S, NH or N (alkyl); and R ' ₇ 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, aroylalkenyl, dialkoxyphosphinylalkyl, diaryloxyphosphinylalkyl, hydroxyalkylthioalkyl, hydroxyalkylsulfonylalkyl, alkoxyalkylthioalkyl, alkoxyalkylsulfonylalkyl, poly (oxyalkylene) alkyl, cyanoalkyl, nitroalkyl, 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. 5. The method, labeled in accordance with claim 1 characterized dad urch that the compound has the following formula: ^{2 <} 9 R ' ₈ - Y' ₃ g - C - CH ₂ - C - NH, Z'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, nitro, cyano,
Dialkoxyphosphinyl, acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino, sulfonylamino, alkylsulfonylamino,
Acyloxy, alkenyl 'or -CH = CHCH = CH-; Y ' _3g is _O , S, NH or N (alkyl); and R 'is a derivative salt or Z with the meaning explained in claim 1, 6.. Process according to claim 1, characterized in that the compound has the formula: Y ¹ R'g - V ₄₀ - C - C - C - NH in which represent: Z 'Q is the same or different and is one or more of hydrogen or substituted or unsubstituted halo, haloalkyl, polyhaloalkyl, polyhaloalkoxy, alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfonyl, finyl, aryl, aryloxy, arylthio, arylsulfonyl, nitro, cyano, dialkoxyphosphinyl, acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino, sulfonylamino, alkylsulfonylamino, acyloxy, alkenyl, or -CH = CHCH = CH-; Y ¹ ^ ₀ is O, S, NH or N (alkyl); , Y '* and Y' are independently hydrogen or substituted halogen, alkyl, alkenyl, alkynyl, alkoxy, alkylthio, cyano, nitro, formyl, amino, hydroxy, alkylcarbonyl, dialkoxyalkyl, alkylcarbonyloxyamino, formylamino, hydroxyalkyl, polyhaloalkyl or haloalkyl ; or Y * and Y ' ₅ 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 non-aromatic ring system, and a bridging ring system. which may be saturated or unsaturated, 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 alkyl, Diaryloxyphosphinylalkyl, hydroxyalkylthioalkyl, Hydroxyalkylsulfonylalkyl, Alkoxyalkylthioalkyl, Alkoxyalkylsulfonylalkyl, poly (oxyalkylene), cyanoalkyl, nitroalkyl, alkylideneamino, carbamoylalkyl, alkylcarbamoylalkyl, dialkylcarbamoylalkyl, aminoalkyl, acylaminoalkyl, acyloxyalkyl, alkoxycarbonylaminoalkyl, Cyanoaminoalkyl, carbamoyloxyalkyl, Alkylcarbamoyloxyalkyl, Dialkylcarbamoyloxyalkyl, alkoxycarbonyloxyalkyl, Alkoxycarbonylthioalkyl, aminosulfonylalkyl , Alkylamino 257 57 sulfonylalkyl or dialkylaminosulfonylalkyl; wherein the permissible substituents Z with the in claim 1 are explained meaning. 7. The method according to claim 1, characterized in that the compound has the following formula: γ · «- c - c - ν -C-C-C-N ^Rt io in which represent: Z'j is the same or different and is one or more of hydrogen or substituted or unsubstituted halogen, haloalkyl, polyhaloalkyl, polyhalogenoalkoxy, 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'-g is hydrogen or alkyl; Y ' ₇ , Y'g * Y'g and Y'-Q are independently hydrogen, halogen or alkyl; Y _'41 is O, S, NH or N (alkyl); and R 'Q 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, aroylal- kyl, Dialkoxyphosphinylalkyl, Diaryloxyphosphinylalkyl, hydroxyalkylthioalkyl, Hydroxyalkylsulfonylalkyl, Alkoxyalkylthioalkyl, Alkoxyalkylsulfonylalkyl, poly (oxyalkylene) alkyl, cyanoalkyl, nitroalkyl, alkylideneamino, carbamoylalkyl, Alkylcarbaraoylalkyl, dialkylcarbamoylalkyl, aminoalkyl, acylaminoalkyl, acyloxyalkyl, alkoxycarbonylaminoalkyl, Cyanoarainoalkyl, carbamoyloxyalkyl, Alkylcarbamoyloxyalkyl, Dialkylcarbamoyloxyalkyl, alkoxycarbonyloxyalkyl Alkoxycarbonylthioalkyl, aminosulfonylalkyl, alkylaminosulfonylalkyl or dialkylaminosulfonylalkyl; wherein the permissible substituents Z are as defined in claim. 8. The method according to claim 1, characterized in that the compound has the following formula: ΐ4; CC \ Υ ' ^XY 12 12 - ^v - ^ "11 - ^Y 'l2" ^C C - NH - J' II Il ο ο in which represent: Z * 2 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 'll' ^Y 'l2 * ^Y' L3 ^'Υ> 14' ^Y 'l5 ^{and Y'} l6 ^{are inde} 9 ^x 9 is hydrogen, halogen or alkyl; Y * ₄₂ is O, S, NH or N (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, hydroxyalkylthibalkyl, hydroxyalkylsulfonylalkyl, alkoxyalkylthioalkyl, alkoxyalkylsulfonylalkyl, poly (oxyalkylene) alkyl, cyanoalkyl, nitroalkyl, alkylideneamino, carbamoylalkyl, alkylcarbamoylalkyl, dialkylcarbamoylalkyl, aminoalkyl, acylaminoalkyl, acyloxyalkyl, alkoxycarbonylaminoalkyl, cyanoarainoalkyl , Carbamoyloxyalkyl, alkylcarbamoyloxyalkyl, dialkylcarbamoyloxyalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonylthioalkyl, aminosulfonylalkyl, alkylaminosulfonylalkyl or dialkylaminosulfonylalkyl; wherein the permissible substituents Z are as defined in claim. 9. The method according to claim 1, characterized in that the compound has the following formula: Y'Y * 20 j 18 K "" Y j -9 ^ * C "" O "* C ™ * in which represent: Z '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, sulfonylaraino, alkylsulfonylamino, acyloxy, alkenyl or -CH = CHCH = CH-; Y ' ₇ is hydrogen or alkyl; Y 'g, ^Y' ig ^{"Y <20 unc} * ^Y * 2l * ^sinc independently hydrogen, halogen or alkyl; Y _'43 is 0, S, NH or N (alkyl); and R _'12 ^{is a} derivative salt or 2 as defined in claim 1. 10, Method according to claim 1, characterized in that ^Z 'l4 ^RI 13 ~ ^ΥΙ 44 * ^C I! in which represent: Z ' ₄ is the same or different and is one or more of hydrogen or substituted or unsubstituted halo, haloalkyl, polyhaloalkyl, polyhaloalkoxy, alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfonic nyl, aryl, aryloxy, arylthio, arylsulfonyl, nitro, cyano, dialkoxyphosphinyl, acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl, acylamino, sulfonylamino, alkylsulfonylamino, acyloxy, alkenyl or -CH = CHCH = CH-; ₂₁ V, Y * 22 '* ^Y 23''24 ^Y * ^Y * ^Y * 25 ^and 26 ^{are inde i} 9 9 is hydrogen, halogen or alkyl; Y ' ₄ is O, S, NH or N (alkyl); and R ¹ , is a derivative salt or Z having the meaning explained in claim 1. 11. The method according to claim 1, characterized in that the compound has the following formula: 14 ^Y 45 over ^Y 27 in which represent: Z " ₅ 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 _'27 is O, S, NH or N (alkyl); Y _'28 includes 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 ring system aromatic or non-aromatic ring system and a bridging ring system which may be saturated or unsaturated; V ₄₅ is O, S, NH or N (alkyl); and R 'is a derivative salt or Z having the meaning explained in claim 1. 12. The method according to claim 1, characterized in that the compound has the following formula: γι γι ^Y 31 ^Y 30 in which represent: Z * 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, nitro, cyano, dialkoxyphosphinyl, Acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl. Acylamino, sulfonylamino, alkylsulfonylamino, acyloxy, alkenyl or -CH = CHCH = CH-; Y ' _2g is _O , S, NH or N (alkyl); - Y 'Q and y * X ₁ are independently hydrogen or substituted or unsubstituted halo, alkenyl, alkynyl, alkyl, alkoxy, alkylthio, cyano, nitro, formyl, amino, hydroxy, alkylcarbonyl, dialkoxyalkyl, alkylcarbonylamino, formylamino. Hydroxyalkyl, polyhaloalkyl or haloalkyl; or Y ' _o and V ₃₁ may be linked together to a substituted or unsubstituted, carbocyclic or heterocyclic ring system selected from a monocyclic aromatic or non-aromatic ring system, a bicyclic aromatic or non-aromatic ring system, a polycyclic aromatic or non-aromatic ring system, and a bridging ring system which may be saturated or unsaturated; V ₄₅ is 0 ,. S, NH or N (alkyl); and R 'is a derivative salt or Z having the meaning explained in claim 1. 13. The method according to claim 1, characterized in that the compound has the following formula: γι γ. ³ \ / ³³ 0 0 in which represent: Z * - 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 _'32 is O, S _{1 is} N or N (alkyl); Y * and Y ' ₄ are independently hydrogen or substituted or unsubstituted halo, alkyl, alkoxy, alkylthio, polyhaloalkyl or haloalkyl; or 257 5? γ ¹ , and Y '. 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, NH or N (alkyl), and R '_ 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 · ^{! 7} \ / ³⁵ Oi wi r \ / - »ρ w ι ρ · ^K 18 ^Y 48 ^Y 35 ^{K ü ü} ° 17 in which represent: R " j 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 _'35 is O ₁ S, N or N (alkyl); Y ' ₆ and Y' ₇ are independently hydrogen or substituted or unsubstituted halo, alkenyl, alkynyl, alkyl, alkoxy, alkylthio, cyano, nitro, formyl, amino, hydroxy, alkylcarbonyl, dialkoxyalkyl, alkylcarbonylamino, formyl 257 57 * amino, hydroxyalkyl, polyhaloalkyl or haloalkyl; or Y'-zfi ^{unQl γ} '-ς7 may be linked together to 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 non-aromatic ring system and a bridging ring system which may be saturated or unsaturated; V ₄₈ is O, S, N or N (alkyl); and R "o is a derivative salt or Z having the meaning explained in claim 1. 15. The method according to claim 1, characterized in that the compound has the following formula: CH ₃ CH ₂ - 0 - C - CH ₂ - C - NH 16. The method according to claim 1, characterized in that the compound has the following formula: HO-C-CH ₂ -C-NH 17. The method according to claim 1, characterized in that the compound has the following formula: Br CH ₃ CH ₃ CH ₂ -O-CCC-NH - (' - Br 18. The method according to claim 1, characterized in that the compound has the following formula: CH ₃ CH ₂ -OCCC-NH br 19. The method according to claim 1, characterized in that the compound has the following formula: V / HO-C-C-C-NH 20. The method according to claim 1, characterized in that the compound has the following formula: HO-C-C-C-NH Cl 21. The method according to claim 1, characterized in that the compound has the following formula: HO-C-C-C-NH - Br 22. The method according to claim 1, characterized in that the compound has the following formula: \ 7 HO-C-C-C-NH Cl 23. The method according to claim 1, characterized in that the compound has the following formula: HO-C-C-C-NH 24. The method according to claim 1, characterized in that the compound has the following formula: CH ₃ CH ₂ - 0 - C - CH ₂ -C-NH-C> - Br 25. A method for increasing the crop yield, characterized in that on the crop an effective, sufficient to increase yield amount of a compound according to claim 33 is aufgebreiht. A method according to claim I _1, characterized in that the compound is applied to the crop in an amount sufficient to increase the yield without causing substantial phytotoxicity. 27. The method according to claim 1, characterized in that the compound is applied to the crop at a time prior to the reproductive growth phase of the plant. 28. The method according to claim 1, characterized in that the compound is applied at a time during the reproductive growth phase of the plant. 29. A method according to claim 1, characterized in that the compound is applied to the plant in a concentration of between about 0.001 and about 100 pounds of the compound per acre. A method according to claim 1, characterized in that the compound is applied to the crop in a concentration between about 0.01 and about 15 pounds of the compound per acre. 31. The method according to claim 1, characterized in that it is the crop to a crop, ornamental plant or grass for agriculture or horticulture. 32. The method according to claim 1, characterized in that the crop has been selected from corn, cotton, sweet potatoes, white potatoes, alfalfa, wheat, rye, rice, barley, oats, millet, dried beans, soybeans, sugar beets, sunflowers, tobacco, tomatoes, Canola, sloping fruits, citrus fruits. Tea, coffee, olives, pineapple, bananas, sugar cane, cocoa, oil palms, herbaceous Outdoor plants, woody shrubs »Grass, ornamentals, evergreens, trees and flowers. 33. Composition for increasing crop yield, kjmn dadujrcii that it contains a suitable vehicle and an effective, sufficient to increase the yield of a sufficient amount of a compound which is selected from the following: 0 H ^R 6 - ^Y 12 - ^C - ^CH 2 * 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 = CHCH = CH-; η is a value between 0 and 5; Y ₁ is O, S or NR ₇ , wherein R _{7 is} hydrogen or alkyl; Y ₂ is O, S, NH or N {alkyl); and R _fi is ammonium, alkylammonium, polyalkylammonium, hydroxyphenylalkylammonium, poly (hydroxyalkyl) aramonium, an alkali metal or alkaline earth metal or substituted or unsubstituted 257 57 tes hydroxyalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkylaminoalkyl, dialkylaminoalkyl, aryl, mercaptoalkyl, alkylthioalkyl, arylthioalkyl, aryloxyalkyl, alkylsulfonylalkyl, alkylsulfinylalkyl, acylalkyl "aroylalkyl, dialkoxyphosphinylalkyl, diaryloxyphosphinylalkyl, hydroxyalkylthioalkyl; Hydroxyalkylsulfonylalkyl, alkoxyalkylthioalkyl, alkoxyalkylsulfonylalkyl, poly (oxyalkylene) alkyl, cyanoalkyl »nitroalkyl, alkylidenaraino, carbamoylalkyl, alkylcarbamoylalkyl» dialkylcarbamoylalkyl, aminoalkyl, acylaminoalkyl, acyloxyalkyl, alkoxycarbonylaminoalkyl, cyanoaminoalkyl, Carbamoyloxyalkyl, alkylcarbamoyloxyalkyl, dialkylcarbamoyloxyalkyl, alkoxycarbonyloxyalkyl, alkoxycarbonylthioalkyl , aminosulfonylalkyl, alkylaminosulfonylalkyl or dialkylarainesulfonylalkyl; γ γ ^R 1 O - ^Y 18 - ^C - ^C - ^C - ^Y 17 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 = CHCH = CH-; η is a value between 0 and 5; Y ₁₇ is O, S or NR ₁₁ , wherein R _{11 is} hydrogen or alkyl; Υ, - is O or S; Y ₁ Q and Y ₂ Q 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; and 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 ,. alkyl Hydroxyalkylsulfonylalkyl, Alkoxyalkylthioalkyl, Alkoxyalkylsulfonylalkyl, poly (oxyalkylene), cyanoalkyl, nitroalkyl, 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. A composition according to claim 33, characterized in that the active compound has the formula: O 0 Il II R ₆ - Y ₁₂ - C - CH ₂ - C - in which represent: Z is independently substituted or unsubstituted halo, haloalkyl, polyhaloalkyl, polyhaloalkoxy, alkyl, alkoxy, alkylthio, alkylsulfonyl, alkylsulfinyl, aryl, aryloxy, arylthio, arylsulfonyl, nitro, cyano, di-alkyl alkoxyphosphinyl. Acyl, aroyl, alkoxycarbonyl, alkoxycarbonylalkyl. Acylamino »sulfonylamino, alkylsulfonylamino, acyloxy, alkenyl or -CH = CHCH = CH-J η is a value between 0 and 5; ^Y ll ^is "° * ^{S or NR} 7" where R _{7 is} hydrogen or alkyl; Y ₂ is O, S _# NH or N (alkyl); and R _c is ammonium, alky! Ammonium, polyalkylammonium> hydroxy Alkylammonium _r poly (hydroxyalkyl) ammonium _{t is} an alkali metal or alkaline earth metal or substituted or unsubstituted. hydroxyalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkylaminoalkyl, dialkylaminoalkyl, aryl, mercaptoalkyl, alkyltbioalkyl, arylthioalkyl, aryloxyalkyl, alkylsulfonylalkyl, alkylsulfinylalkyl, acylalkyl, aroylalkyl, dialkoxyphosphinylalkyl, diaryloxyphosphinylalkyl, hydroxyalkylthioalkyl, hydroxyalkylsulfonylalkyl, alkoxyalkylthioalkyl, alkoxyalkylsulfonylalkyl, poly (oxyalkylene) alkyl, cyanoalkyl, Nitroalkyl, 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 33, 35. A composition according to claim 33, characterized in that the active compound has the formula: - 26a - ^Y 20
\ ^R 1Ö - ^Υ 18 - C - C - C »Jt OO 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 = CHCH = CH-; - η is a value between 0 and 5; ' Y ₁₇ is O, S or NR ₁₁ , wherein R _{11 is} hydrogen or alkyl; Y ₁₀ is 0 or S; Y ₁ Q and Y ₂ Q 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, and R ₁₀ is hydrogen, ammonium, alkylammonium, polyalkylamraonium, 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, nitroalkyl, alkylideneamino, carbamoylalkyl, alkylcarbamoylalkyl, dialkylcarbamoylalkyl, aminoalkyl, acylaminoalkyl, acyloxyalkyl, alkoxycarbonyl, aminoalkyl, Cyanoaminoalkyl, carbamoyloxyalkyl, alkylcarbamoyloxyalkyl, dialkylcarbamoyloxyalkyl, alkoxycarbonyl - 28 - oxyalkyl, alkoxycarbonylthioalkyl, aminosulfonylalkyl, alkylaminosulfonylalkyl or dialkylaminosulfonylalkyl; wherein the permissible substituents Z are as defined in claim 33 meaning. A composition according to claim 33, characterized in that the active compound has the formula: V7 HO-C-C-C-NH u η O 0 37. The method according to claim 1, characterized in that the compound is used in combination with one or more other biologically active compounds. 38. The method according to claim 1 _# characterized in that it is the compound is a derivative salt. 39. The method of claim 38, 9 ^ | Ji®0G ^: ^? -? 'L ⁿ ®? in that the derivative salt is selected from an alkali metal, an alkaline earth metal, ammonium, alkylammonium, polyhaloalkylammonium hydroxyalkylammonium, poly (hydroxyalkyl) ammonium or mixtures thereof.