DD257573A5 - HERBICIDAL AGENT - Google Patents

Abstract

There are described herbicidal compositions containing N- (5-substituted methylene) phenyl compounds as active ingredient and the excellent pre-emergence Bekaempfung of broad-leaved weevils and Graesern at such low rates of application as 0.28 kg / ha result with a very good security against it Soybeans, cotton, corn and wheat. In post-emergence treatment, these compounds show excellent and rapid control of broadleaf weeds with little (0 to 20%) damage to soybeans, corn, wheat and rice at as low as 0.017 kg / ha. The compounds of the invention provide improved safety over crops and control of grassy weeds. New aniline intermediates for the preparation of the anilides are also described.

Description

Field of application of the invention

The invention relates to herbicidal compositions which in particular allow excellent control of broadleaf weeds and grasses.

Characteristic of the known state of the art

It is known that N-aryl-3,4,5,6-tetrahydrophthalimides are useful as herbicides; see, for. No. 4,201,272 and JP-OS J54019-965, published July 12, 1977. Herbicidal tetrahydrophthalimides substituted in the C ₅ position of the aryl ring by, inter alia, alkoxy, amino, carboxyl or thio groups z. As disclosed in EP-A-061,741, published October 6, 1982, EP-A-0 049 508, published April 14, 1982, EP-A-0 077 938, published May 4, 1983, EP-A-0 8 0 055 on July 6, 1983, EP-A-0 126419 published on November 28, 1984 and JP-OS J9155358 published on September 4, 1984

 EP-A-0 086 822 discloses the following compound:

Object of the invention

The aim of the invention is the provision of new effective agents for controlling weeds, in particular for the selective control of weeds in crops.

Explanation of the essence of the invention

In the general form, the invention relates to herbicidal compositions containing novel anilide compounds and to processes for preparing these compounds. The compounds contained in the agents according to the invention are N- (5-substituted methylene) phenyl herbicides of the formula:

in the:

Ri and R2 independently of one another mean:

Is hydrogen, halogen, (C ₁ -C ₃ ) -alkyl, (C ₁ -C ₃₎ -alkoxy, trifluoromethyl, phenoxy or benzyloxy, where the phenyl ring may be substituted by halogen, (C ₁ -C ₃ ) -alkyl, alkoxy , Cyano, nitro, alkylthio or haloalkyl groups; R ₃ and R _4, independently of one another, denote hydrogen, C 1 -C 8 -alkyl, alkenyl or alkynyl or halogen:

Y contains not more than 10 aliphatic carbon atoms and means:

Hydrogen, halogen, cyano, nitrate, C 1 -C 6 -alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, cycloalkenylalkyl,

Hydroxy, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, cycloalkyl-alkoxy, cycloalkenyloxy, hydroxyalkyl, alkoxyalkyl,

Alkenyloxyalkyl, alkynyloxyalkyl, cycloalkyloxyalkyl,

d-Cs-alkylthio, alkenylthio, alkynylthio, cycloalkylthio, cycloalkenylthio, alkylthioalkyl, alkenylthioalkyl, alkynylthioalkyl, phenyl, phenoxy or phenylthio, where the phenyl ring may be substituted by one or more halogen atoms,

lower alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl groups.

Alkoxycarbonyl, cycloalkyloxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, alkoxycarbonylalkoxy, cycloalkyloxycarbonylalkoxy, alkenyloxycarbonylalkoxy, alkynyloxycarbonylalkoxy, alkoxycarbonyloxy,

Cycloalkyloxycarbonyloxy, Alkenyloxycarbonyloxy, Alkinyloxycarbonyloxy, Alkyicarbonyl, cycloalkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, alkenylcarbonyloxy, Alkinylcarbonyloxy, Alkylcarbonylalkoxy, Cycloalkylcarbonylalkoxy, Alkenylcarbonylalkoxy, Alkinylcarbonylalkoxy, alkylcarbonylalkyl, Alkenylcarbonylalkyl, Alkinylcarbonylalkyl, cycloalkylcarbonylalkyl, alkoxycarbonylalkyl, Alkenyloxycarbonylalkyl, Alkinyloxycarbonylalkyl, Cycloalkyloxycarbonylalkyl, alkylcarbonyloxyalkyl, alkenylcarbonyloxyalkyl, Alkinylcarbonyloxyalkyl,

Cycloalkylcarbonyloxyalkyl, alkoxycarbonyloxyalkyl, alkenyloxycarbonyloxyalkyl, alkynyloxycarbonyloxyalkyl, cycloalkyloxycarbonyloxyalkyl, alkoxycarbonylalkylcarbonyloxy, haloalkylcarbonyloxy, haloalkoxy, alkoxyalkoxy, cyanoalkoxy, phenylcarbonyloxy, phenoxycarbonyloxy,

Phenylcarbonylalkoxy, phenoxycarbonylalkoxy, phenylcarbonylalkylthio, phenoxycarbonylalkylthio, wherein the phenyl ring

each may be substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl, alkoxycarbonylalkylthio, alkenyloxycarbonylalkylthio, alkynyloxycarbonylalkylthio, cycloalkyloxycarbonylalkylthio, alkylcarbonylalkylthio, alkenylcarbonylalkylthio, alkynylcarbonylalkylthio, cycloalkylcarbonylalkylthio, alkylthioalkoxy,

alkoxyalkylthio,

Alkylthioalkylthio, haloalkylthio,

Alkylsulfinyl, alkenylsulfinyl,

Alkynylsulfinyl, cycloalkylsulfinyl, phenylsulfinyl, phenylsulfinyl substituted by halogen, lower alkyl, lower alkoxy,

Cyano, nitro, alkylthio or haloalkyl groups,

Alkylsulfonyl, alkenylsulfonyl, alkynylsulfonyl, cycloalkylsulfonyl, phenylsulfonyl, phenylsulfonyl substituted by halogen,

lower alkyl, lower alkoxy, cyano, nitro or haloalkyl groups.

Alkoxycarbonylalkylsulfinyl, Alkenyloxycarbonylalkylsulfinyl / Alkinyloxycarbonylalkylsulfinyl, Cycloalkyloxycarbonylalkylsulfinyl, Alkylcarbonylalkylsulfinyl, Alkenylcarbonylaikylsulfinyl, Alkinylcarbonylalkylsulfinyl, Cycloalkylcarbonylalkylsulfinyl, Alkoxycarbonylalkylsulfonyl, Alkenyloxycarbonylalkylsulfonyl, Alkinyloxycarbonylalkylsulfonyl, Cycloalkyloxycarbonylalkylsulfonyl, Alkylcarbonylalkylsulfonyl, Alkenylcarbonylalkylsulfonyi, Alkincarbonylalkylsulfonyl, Cycloalkylcarbonylalkylsulfonyl,

(eg ^ -C-SCH-),

alkylthiocarbonyl

Alkenylthiocarbonyl, alkynylthiocarbonyl, cycloalkylthiocarbonyl, phenylthiocarbonyl, phenylthiocarbonyl substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl groups,

Alkylthiocarbonyloxy (eg 0-C ₂₃

Alkenylthiocarbonyloxy, alkynylthiocarbonyloxy, cycloalkylthiocarbonyloxy, phenylthiocarbonyloxy, phenylthiocarbonyloxy substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkylthio, or haloalkyl groups,

Alkylthiocarbonyloxyalkyi ^(Z * ^B * ^ 2 ° ^C " ^SCH ₃ >'

Alkenylthiocarbonyloxyalkyl, alkynylthiocarbonyloxyalkyl, cycloalkylthiocarbonyloxyalkyl, phenylthiocarbonyloxyalkyl,

Phenylthiocarbonyloxyalkyl,

where the phenyl ring is substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl groups,

Amino, aminocarbonyl, aminocarbonyloxy,

Aminothiocarbonyloxy, aminocarbonylalkoxy,

Äminocarbonyloxyalkyl, Aminothiocarbonyloxyalkyl or Äminocarbonylalkylthio, wherein

(a) the amino group may each be substituted by up to 2 substituents independently selected from: alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkoxyalkyl, alkoxycarbonylalkyl, alkenyloxyalkyl, alkynyloxyalkyl, phenyl or phenyl substituted by halogen,

lower alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl groups, or

(b) the amino group has two substituents which, together with the amino nitrogen, form a 5- to 6-membered heterocyclic ring containing 0-3 further heteroatoms selected in any combination from the group consisting of oxygen, nitrogen and sulfur,

Aminocarbonylalkylamino, where the amino groups may be independently substituted by 0 to 2 alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyalkyl, phenyl or phenyl substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl groups,

An aminocarbonylalkylamino wherein the terminal amino group has two substituents which, together with the terminal amino nitrogen, form a 5- to 6-membered ring containing 0-3 further heteroatoms selected in any combination of the group consisting of oxygen, nitrogen and sulfur , Alkylcarbonylalkylamino, alkoxycarbonylalkylamino, phenylcarbonylalkylamino and phenoxycarbonylalkylamino wherein the amino group may each be substituted by an alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyalkyl, phenyl or phenyl substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl groups, phenoxycarbonylalkylamino, wherein the amino group is substituted by Obis 1 alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyalkyl, phenyl or phenyl substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl groups , and the phenoxy group is substituted by halogen, never alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl groups,

Alkoxycarbonylalkylaminocarbonyl, where the amino group may be substituted by an alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyalkyl, phenyl or phenyl substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl groups,

oximino

Alkoxycarbonyloximino,

Alkoxycarbonyloximinocarbonyl,

any 5- or 6-membered heterocycle containing one to three oxygen, nitrogen or sulfur atoms, any of the following functional groups:

ο 'ο

/ -0R ₅ , «/ -R ₇

- C - R ₆ , - CR ₆ , - C - R _fi

C-OR ₅ S- ^0R 5 C-OR ₅

Il

0 0

CN ^c " ^NR 8 ^R 9

C -% · * C - R ₆ , - 0 (CH ₂ ) n CO ₂ ^G Q®

C - NRoR

11

0 (CH ₂ ) n - C -

⁰ N

-S-C-N

R.

S -S-C-n '

R. Rf

R, ρ

-ν- c-N:

- S (CH ₂ ) η C0 ₂ ° Q®

- OCH ₂ CH - CH

- 0 (CH ₂ ) n N

Χ®

- OCH ₂ CH - CH ₂ O

3CH ₃ CH ₃

- OCH ₂ CH - CH ₂ OH OH

- 0 - P

- 0 - P

OCH ₂ CH ₂ -N

or-O-glycoside

-CPs-CH-CH ₀ CH,

I ^{2 2 3} 0 -CH ₂ CH ₃

at them:

R _{5 is} C 1 -C 6 -alkyl, cycloalkyl, alkenyl, alkynyl or cycloalkenyl 1st;

R ₆ and R _{7 are} independently hydrogen, C ₁ -C ₆ alkyl, cycloalkyl, alkenyl, alkynyl, cycloalkenyl, phenyl or phenyl substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or Haloalkyl groups, R ₈ and R _{9 is} hydrogen, C ₁ -C ₆ alkyl, cycloalkyl, alkenyl, alkynyl or cycloalkenyl; η is an integer from 1 to 4;

Q is an alkali or alkaline earth metal cation (e.g., Na ⁺ , K ⁺ , Ca ⁺² ) or a cation derived from an inorganic or organic base, e.g. B. NHY, Et means ₃ ®NH or pyridinium;

X is an anion, preferably derived from a strong acid, eg, halogen, sulfate or hydroxide; R _{10 is} C ₁ -C ₆ -alkyl, cycloalkyl, alkenyl or cycloalkenyl;

-O-glycoside is any sugar group attached to the C ₅ methylene via a glycoside bond, the sugar being in the free hydroxy form

orwherein the sugar has free hydroxyl groups attached to protecting groups such as isopropylidene groups: e.g.

Z is a heterocyclic ring system attached to the phenyl ring via a nitrogen atom which is also part of the ring system or a carbocyclic or heterocyclic ring system attached to the ring via a nitrogen atom which is not part of the ring system.

When in the above formulas R ₁ and / or R _{2 is} halogen, fluorine, chlorine and bromine are preferred. Unless otherwise indicated, aliphatic and cycloaliphatic groups preferably contain not more than 10 carbon atoms. For example, in the formulas given above, Z may be a heterocyclic ring system containing only one heteroatom in the ring, namely the nitrogen atom which binds the ring system to the phenyl ring. Examples include:

Z may also contain two identical heteroatoms in the ring, such as:

Ö

W A '

.cl

BC

A '

three identical heteroatoms, such as:

R

O-.

rX

N ·

Λ "-

or two or more heteroatoms that are different, such as:

Z may also be a carbocyclic ring system attached to the phenyl ring via an amide or thioamide nitrogen atom (which is not part of the ring system), such as:

α CN C-NH-

N C

Il I!

O O

-NH-

or a heterocyclic ring attached to the phenyl ring via a nitrogen atom which is not part of the ring, such as:

In the examples given above for Z, A and A 'are independently oxygen, sulfur or -NR; B and D are independently oxygen, sulfur or NR, wherein R is as defined below; E is halogen, hydroxy, alkyicarbonyloxy,

Alkoxycarbonyloxy, alkylcarbonylthio,

Alkoxycarbonylthio, alkoxy, alkenyioxy, alkynyloxy, amino, alkylamino, dialkylamino, mercapto, alkylthio, alkenylthio, alkylsulfinyl or alkylsulfonyl, with the proviso that E can not contain more than 10 carbon atoms; G oxygen, nitrogen or sulfur in any oxidation state;

J Hydroxy or salts derived therefrom (eg salts with alkali and alkaline earth counterions such as Na ⁺ , K ⁺ or Ca ⁺² and salts with organic counterions such

(C ₂ H ₅ I ₃ NH, pyridinium, NH ₄ , etc.);

Alkoxy, alkenyioxy, alkynyloxy, cycloalkyloxy, cycloalkenyloxy,

Phenoxy, phenoxy substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl groups,

Amino, alkylamino, dialkylamino, alkenylamino, dialkenylamino, alkynylamino, morpholino, pyrrolidino, hydrazino, alkylhydrazino, unsymmetrical dialkylhydrazino, phenylhydrazino, phenylhydrazino, whose phenyl ring is substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or Haloalkyl groups, cycloalkylamino, benzylamino, benzylamino whose phenyl ring is substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl groups;

with the proviso that J can not contain more than 10 aliphatic carbon atoms; R, R11-R16, Ri8 / Ri9. and R21-R29 are independently hydrogen, alkyl, alkylcarbonyl, alkenyl or alkynyl; Phenyl, which may be substituted by one or more alkyl, cyano, halogen, nitro, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or dialkylamino substituents

with the proviso that R, R ₁₁ -R ₁₆ , R ₁₈ , R ₁₉ , and R _{2 1} -R29 contain not more than 10 aliphatic carbon atoms, and wherein R ₂ 8 is also C 1 -C 6 -alkylthio, alkoxy or mono- or dialkylamino can; R _{17 is} C ₁ -C ₁₀ alkyl, alkenyl, alkynyl or cycloalkyl;

R _{20 is} -CO ₂ R ¹ , wherein R ^{1 is} lower (C ₁ -Ca) alkyl and

η is an integer from 0 to 2.

In the above general formulas, when R _{1 is} hydrogen, R _{2 is} chloro, and R ₃ and R _{4 are} hydrogen, Y may not be cyanomethyl.

In the synthesis of these herbicides, the following new intermediates can be used ·

or

where R ₁ , R ₂ , R ₃ and R ₄ and Y have the abovementioned meaning.

When used after emergence, the compositions of the invention have excellent action in controlling broadleaf weeds at very low effort rates, based on active ingredient (as low as 0.017 kg / ha; 0.0151 b / A), with good selectivity to important ones Useful plants, eg Soybeans, corn, wheat and rice. When treated after emergence for effective control of grass weeds, the compositions of the invention require significantly higher application rates (> 1.1 kg / ha;> 1. 01 b / A). At these higher rates of effort (> 1.1 kg / ha, 1.01 b / A) and above. For example, the agents according to the invention can be used as non-selective total herbicides.

The compositions of the present invention also provide excellent control of broadleaf and grass weeds before emergence, albeit at higher rates of application (0.28 to 1.1 kg / ha, 0.25 to 1.01 b / A) than those used to control broadleaf Weeds are required after emergence. When these pre-emergence treatments are applied, they are relatively safe against soybeans, cotton, corn, wheat and other crops. A significant advantage of the agents of the invention is that they allow the control of both broadleaf and grass weeds. Thus, when using the agents according to the invention, the farmer can avoid the use of complex tank mixtures consisting of two or more herbicides.

The Cs-substituted methylene-anilides contained in the agent according to the invention are further illustrated by the following compounds, as indicated in lists A-F.

List A

A R

CH.

O O

Cl

-OCHCH CH

O O

Cl

O O

Cl

List A (continuation)

Aft ·

0 0

Cl H

CH.

-OCH OCH

O O

Cl H

-OCH CH (CH )

O O

Cl H

CH.

-OCH = CH-C

O O

Cl H

-OC (CH) CCH

O O

O O

Cl

Cl H

-OCH CH = CH-CH = CH

OCH.

O O

O O

Cl H

Cl H

CH ₃

Cl

ο ο ο ο

F - Cl H H

F Cl H H

-CH CH = CH 2

O O

Cl

-CH C = CH

O O

O O

Cl H

Cl H

-C = CH

Cl

List A (continued)

ft A ¹

R ₂ R ₃ ^R ₄

0 0

Cl H

CF ₁

0 0

Cl H

0 0

Cl H

-SCH C = CH

0 0

Cl H

-O

O O

Cl H

ο o

Cl H

O O

Cl H

CH.

O O

Cl H

-N-CH CH

* A '

List A (Continued

0 0

Cl H

CH ₃

-Al-CH ₂ C = CH

0 0

Cl H

0 0

Cl H

-OCH ₂ C-OCH (CH

O O

Cl H

9 ^Η 3 8 Χ.Η - C-

-OCH-C-OCH ₃

0 0

Cl H

O O

Cl H

· SCH -

ο o

Cl H

-S (CH ₂ ^ ₃ C-OCH ₃

O O

O O

Cl H

Cl H

9

C O

-OCH ₂ C-NH - // X) -Cl

List A (continued)

9% rh * ⁴ V i A

9 93

0 0 F Cl HH -SCH ₂ CN-CH ₂ CH ₃

0 0 F Cl HH -OW = C-CH ₃

0 0 F Cl HH -OPi = CH-C-OCH ₂ CH ₃

CH ₃ 0 0 F Cl HH -OCHCH ₂ Cl

ü 0 F Cl HH -SCH ₂ CH ₂ Cl

0 0 F Cl HH. ' -OCH ₂ CH ₂ UCH ₃

0 0 F Cl HH -OCH ₂ OCH ₂ CH ₃

0 0 Γ Cl HH -OCH ₂ SCH ₃

0 0 F Cl HH -OCH ₂ SCH (CH ₃ ^ ₂

List A (continued)

A 'R ₁ R ₂ R ₃

0 0 F Cl HH -SCH ₂ CH ₂ OCH ₃

0 0 F Cl HH -SCH ₂ CH ₂ SCH ₃

0 0 F Cl HH -OCH ₂ CH ₂ CH ₂ CN

0 OF Cl HH -OCH ₂ C-CHfCH ₃ "

Cl

οη η η -OCh ₂ C ¹ -ο- / ' yc \

OOF Cl HH -OCH ₂ C ¹ -O- / J

0 0 F Cl HH - -SCH ₂ CH ₂ C-CH ₃

OOF Cl HH -SCH ₂ CH ₂

C!

0 OO F Cl HH -SCH ₂ CO-

lf \ a

OOF Cl HH -WHCH ₂ COCH ₂ CH ₃

A A «

List A (continued)

0 0

Cl H

CH ₃ O

NCH ₂ COCH ₂ CH ₃

0 0

Cl H

0 SCH ₂ CH ₃

0 0 F, Cl H ft -S-CH (CH ₃

0 0

Cl H -SO ₂ CH (CH ₃ ^ ₂

0 0 0 0

Cl H

Cl H

Cl

0 0

Cl H -S-CH ₂ C-OCH ₂ CH ₃

ο o

Cl HH -SO ₂ CH ₂ C-OCH ₂ CH ₃

0 0 Cl H

-NHCH ₂ CH ₂ C * -CH ₃

A A '

List A (continued)

0 0

Cl H

OO

Cl H

P ₁

-N (CH ₃ ) CH ₂ C-

0 0 F Cl H H

-N (CH ₃ ) CH ₂ U-N (CH ₃ ) ₂ "

0 0

Cl H

0 CH ₃ / Γ ~ Λ -N (CH ₃ KH ₂ CN- (ZV |

0 0

Cl H

-CH (COCH ₃ ) ₂

0 0

Cl H

-C (C ¹ OCH ₂ CH ₃ )

0 0

Cl

-CH (CN) (CO ₂ CH ₂ CH ₃ )

0 0

Cl H

-CH (COCH ₃ ) (CO ₂ CH ₂ Ch ₃ )

0 0

Cl -C (COCH ₃ ) (CO ₂ CH ₂ CH ₃ ) CH ₂ CrCH

List A (continued)

AA 'R ₁ R ₂ R ₃

0 0 F Cl HH -CHfCN) ₂

0-0 F Cl HH -Cf- / H (CN) ₂

P. 0 0 F Cl H H CfC

OO F Cl HH -CH [i: -N (CH ₃ ) ₂ 3 ₂

0 0 F Cl HH -C (CH ₃ ) [CN (CH ₃ ) ₂ 3 ₂

θ φ

0 0 F Cl HH -O (CH ₂ ) ₄ C0 ₂ NH ₄

0 0 F Cl H H

0 0 F Cl HH -N (CH ₃ ) ₃ C1

0 0 F Cl H H

H ₂ LH

List Ä (continued)

^Ri* z "ι

® θ

0.0 f Cl HH -OiCH2) ₄ M (CH3) ₃ Cl

0 0 P Cl HH -OCH ₃ CH-CH,

* ι * O _x O

^C CH

OH OH 0 0 F "Cl HH -OCH ₂ CH-CH ₂

O OF C H H -O 4

OO F Cl ^HH -O -? Y JI

CH ₃

OOF Cl ^H H -O-PV ^w φ

-0-CH ₂

OO F Cl ^H H ^

oof Ch ₃ hh

from ₃ ^{h to} -h (ch ₃ ) ₂

List A (continued)

AA 'R ₁ ' 2 ^R 3 ^R 4

O O H - CH ₂ 0 // Cl H H O O F Cl F H O O F Cl F F 0 0 F Cl CHj H

0 0 F -O ~ (/ "\ c \ ^H H -OCHfCHj) ₂

0 0 F -CH ₂ O- ^ \ c ^H H -OCH (CHj) ₂

-OCH (CHj) ₂

-OCH (CHj) ₂ -OCH (CH ₃ ) ₂ -OCH (CHj) ₂

0 0 F Cl CH ₃ CHj -OCH (CHj) ₂

0 0 F Cl H -CH ₂ CSJH -OCH (CHj) ₂

0 0 H Cl HH -OCH ₂ UO- / J

0 0 H Cl HH -SCH (CHj) ₂

0 0 H Cl HH -OCH ₂ C = CH

0 0 H Cl Ή Η -0

0 0 H · Cl HH -OCH ₂ COCH (CHj) ₂

S S

S S

List A (continued)

·, ^R ₂ ·,

SO F Cl H H

Cl HH

Cl H H

> 'O' l · Cl H H

S S F Cl HH

-OCH (CH ₃ ) ₂

Cl HH -OCH ₂ CSCH

Cl HH-OCH-CrCH

_Cl HH -OCH ₂ CO- / J "

_Cl HH -OCH ₂ C = CH

SS 'H Cl ^HH -OCH (CH ₃ ^ ₂

9

SSH Cl HH ^ CH ₂ C

AA ¹

List A (continued)

SSH Cl

-OCH ₂ CH ₃

S S

Cl CH ₃

CH ₅

S S

Cl

S O

H-O

-OCH (CH ₃ ) ₂

S 0

-OCH (CH ₃

u -CH ₂ O

- οι - e-jι

List B

C-Y

ti 0

• I- -2- -3- -4-

Cl HH -OCH (CH ₃ ) ₂

Cl H

-OCH ₂ C

it o

Cl H

H -OCH ₂ C = CH

it

Cl HH -OCH (CH ₃ ) ₂

w o

Cl H

it o

Cl H

-OCH (CH ₃ ) ₂

Cl HH -OCH (CH ₃ ) ₂

f ^ YX

O S

co-

co-

ca-

List B (continued)

J? 2_ _? 3- _? 4-

Cl HH

Cl HH -OCH (CH ₃ ) ₂

ν O

Y F Cl H H -OCH

CO-Z j

H CH ₂ O- ^ ^ -Cl HH -OCH (CH ₃ ) ₂

Cl HH -OCH (CH ₃ ) ₂

Cl HH -OCH (CH ₃ ) ₂

Cl HH -OCH (CH ₃ ) ₂

Cl HH -OCH (CHj) ₂

co-

co-

Il

α} -co-

List B (continued)

-Bl- _J2_ -53- _? 4_

F Cl HH -OCH ₂ C = CH

F Cl H H

η. η

IT VF Cl HH -OCH (CH ₃ ) ₂

ch; ..

F Ci HH -OCH (CH ₃ ) ₂

F Cl HH -OCH (CHj) ₂ F Cl HH-OCH (CH ₃ ^ ₂ F Cl HH-OCH (CH ₃ ) ₂

List B (continued)

_ * 2_ J? 3- - * 4-

O>

CH,

Cl

F Cl H H -O-

F Cl HH -OCH (CHj) ₂

Cl

F Cl H H -OCH

K)

F Cl HH -OCH (CH ₃ ^ ₂

CHj O

CH3O-C

F Cl HH -OCH (CHj) ₂

CH3O-C

F Cl H H -O-

CH ₅

CH ₁ D _h

F Cl HH -OCH (CHj) ₂

CH ^ H ₁ S ^

F Cl H H -O-

List B (continued)

CH, CH, S ^K N CH, CHv U CH ₁ O \ > \ CH, O I Il

CH,

-2- -3- -4-

F Cl HH -OCH (CH ₃ ) ₂

F Cl HH -OCH (CH ₃ ) ₂

F Cl H H -O-

Il

F, Cl HH -OCH (CHj) ₂

CH ₁ -CN N-

'V CH, _δ

F Cl HH -OCH (CH ₃ ) ₂

F Cl HH -OCH (CH ₃ ) ₂

cn,

F Cl HH -OCH (CH ₃ ) ₂

Cl HH -OCH (CH ₃ ) ₂

List B (continued)

ö-

Cl H

-OCH (CH ₃ ) 2 Y H

CH ₃ P

O-Cl H

-OCH

Cl HH -OOCH (CH ₃ ) ₂

ti o

I ©

Cl H H Cl H

Cl H H -OCH.

CH, κ

• F Cl HH -OCH (CHj) ₂

List B ( continued)

R, R. _R.

OQ CO

¹ UCH ₁

CO-o>

F Cl HH -OCH (CH ₃ ) ₂

F Cl HH -OCH (CH ₃ ) ₂

F Cl HH -OCH (CH ₃ ^ ₂

F Cl HH -OCH (CH ₃ ) ₂

9

F Cl HH -OCH (CH ₃ ) ₂

F-Cl HH-OCH (CH ₃ ) ₂

Cl HH -OCH (CH ₃ ^ ₂

- OO - C-Jl -J / »J

List B (Continued

Cl

I ₂ . J ₃ . J? ₄ _

η H -OCH (CH ₃ ) -,

Cl HH -OCH (CH ₃ ) ₂

SCH,

or

Cl HH -OCH (CH ₃ ) ₂

Cl HH -OCH (CH ₃ ) ₂

CH ₁

Cl HH ^ XH (CH ₃ ) ₂

AA ¹

OO * OCH ₃

L IST C

NH

-J

- ^R 2

- ^R 3

F Cl HH -OCH (CH ₃ ) ₂

0 0 OCH ₃

Cl HH -OC (CH ₃ ) ₂

0 OCH;

0 0 OCH ₃

Cl H H -OCH

Cl HH -OCH ₂ C = CH

0 0 -OCH ₂ C = CH

0 0

0 0 NH

F Cl HH -OCH (CH ₃ ^ ₂

Cl HH -OCH (CH ₃ ) ₂

Cl HH -OCH (CH ₃ J ₂

0 0 -N (CH ₃ ) 2

Cl HH -OCH (CH ₃ ) ₂

0 0 -NHCH ₂ C = CH

0 0

0 0

-O

Cl HH -OCH (CH ₃ ) ₂

Cl H

Cl H H

List C (continued)

A A '

*1

0 0 -NHN (CH ₃ ¹ J ₂

Cl HH -OCH (CH ₃ ^ ₂

0 0 -NHNH

v A

Cl HH -OCH (CH ₃ ) ₂

0 0

Cl HH -OCH (CH ₃ ) ₂

0 0 OCH ₃

H -OCH ₂ // \\ C | HH -OCH (CH ₃ ) ₂

0 0 OCH ₃

i ^ vlh

H -OCH ₂ C

SS OCH ₃

Cl HH -OCH (CH ₃ ) ₂

SS OCH _:

Cl HH -OCH (CH ₃ ) ₂

0 0 OCH (CH ₃ ) ₂

Cl

H -SCH (CH ₃ ^ ₂

0 0 OC (CH ₃ ) ₃

Cl HH -OCH (CH ₃ ) ₂

0 0 -NHCH (CH ₃ ) ₂

Cl HH -OCH (CH ₃ ) ₂

0 0

Cl HH -OCH ₇ O

List D

ciy

Cl is -OCH (CHj) ₂

Cl

Cl

-OCH ₂ C = CH

Cl

-OC (CHj) ₃

Cl

-SCH (CHj) ₂

Cl

-SCH ₂ CH ₂ OCHj

Cl

-OCH (CHj) ₂

Cl

-OCH ₂ C

Cl

-SCH (CHj) ₂

H -OCH ₂ -

^ y

C \ H -OCH (CHj) ₂

List D (continued)

^! 3- ^: 4-

H -OCH ₂ -V V-Cl H

-SCH (CH ₃ ) ₂

Cl

-OCH (CH ₃ ) ₂

Cl -OCH (CH ₃

Cl -OCH ₂ CO ₂

- / J

Cl

Cl

-OCH ₂ CO ₂ CH ₂ C = CH Cl

Cl

-ON = CH-CO ₂ CH ₂ CH ₃

Cl

-SO ₂ CH (CH ₃ ) ₂

Cl

Φ Θ

-OCH ₂ CH ₂ N (CH ₃ ) ₃ Cl

Cl

-OCH ₂ CH ₂ CH ₂ CO ₂ CH ₃

Cl

Cl

-OCH ₂ CH (CH ₃ ) ₂

RRR -1- 2- 3 "

List E

C-Y

Cl HH -OCH (CH ₃ ) ₂

Cl MM -SCH (CH ₃ ) ₂

Cl HH -OCH ₂ CO- / J

Cl H H

Cl HH -OCH ₂ C = CH

CH ₁

Cl HH -OCHCH ₂ CH ₃

Cl H H

Cl HH -OCH ₂ C (CH ₃ ) 3

CH ₃

Cl HH -OCH ₂ C = CH ₂

Cl _- HH _- OCH ₂ CH (CH ₃ I ₂

List E (continued)

 ι-4

J'-OC

"3H-C = C-H

Cl

Cl

-OCH ₂

he

Cl

Cl

Cl

egg

Cl

Cl

-SC (CH ₃ O ₃

Cl -SCH ₂ C = CH

List E (continued)

- R, R ₄

2 3- 4-

Cl H H

.a w

Cl HH -N [CH (CH ₃ ) ₂ ] ₂

Cl HH -N (CH ₃ ) ₂

CH ₃

Cl HH -N-CH ₂ CH ₃

Cl HH -N-CH ₂ C = CH

Cl H H -N-f /

CH ₃ Cl HH -OCHCO ₂ CH ₃

Cl HH -OC (CH ₃ ) ₂ CO ₂

Cl HH -SCH ₂ CO ₂

Cl HH -OCH ₂ CN (CH ₃ ) j

List E (continued)

J₁,-I ₂ - -J₃-

Cl HH -OCH ₂ C-NH - // N) -Cl

Cl HH -SCH ₂ CN-CH ₂ CH ₃

CH ₃

Cl HH -ON = C-CH ₃

Cl HH -OM = CH-CO ₂ CH ₂ CH ₃

pn

-OCHCI-

Cl HH -OCHCH ₂ Cl

Cl HH -SCH ₂ CH ₂ Cl

Cl HH -OCH ₂ CH ₂ OCH ₃

Cl HH -OCH ₂ OCH ₂ CH ₃

Cl H H- OCH ₂ SCH ₃

Cl HH -OCH ₂ SCH (CH ₃ ^ ₂

Cl HH -SCH ₂ CH ₂ OCH ₃

List E (continued)

Cl HH -SCH ₂ CH ₂ SCH ₃

Cl HH -OCH ₂ CH ₂ CH ₂ CN

Cl HH -OCH ₂ C-CH (CH ₃ ) ₂

Cl

Cl HH -OCH ₂ CO ₂

Cl HH -SCH ₂ CH ₂ C-CH ₃

Cl HH -WHCH ₂ CO ₂ CH ₂ CH ₃

Cl HH -NCH ₂ CO ₂ CH ₂ CH ₃

Cl HH -SCH ₂ CH ₃

0 Cl H H

Cl HH -SO ₂ CH (CH ₃ ) ₂

List E (continued)

 ι-

-3--

"4-

Cl

Cl

-SO ₂ CH (CH ₃ ) ₂ C!

 so / Vci

Cl

H -SO ₂ CH ₂ CH ₃

Cl

-S-CH ₂ -COCH ₂ CH ₃

Cl

H -SO ₂ CH ₂ CO ₂ CH ₂ CH ₃

Cl H -NHCH ₂ CH ₂ C-CH ₃

Cl.

Cl 0 H -N (CH ₃ ) CH ₂ C-CH (CH ₃ )

C!

Cl

-N (CH ₃ ) CH ₂ CN (CH ₃ .

C-N (CH, V

List E (continued)

0 CH ₃ ,

Cl HH -N (CH ₃ KH ₂ SN- (Z ^

Cl H H -CH (COCH,)

3 '2

Cl HH -C (CO ₂ CH ₂ CH ₃ ) ₂

Cl HH -CH (CN) (CO ₂ CH ₂ CH ₃ )

Cl HH -CHiCOCHP (CO ₂ CH ₂ CH ₃ )

Cl HH -C (COCH ₃ ) (CO ₂ CH ₂ CH ₃ )

CH ₂ C = CH

ClHH-CH (CN) ₂

Cl H

Cl HH-CH (CONH ₂ ) ₂

Cl HH -CH [C ^ -N (CH ₃ ) ₂ ] ₂

List E (continued)

J ₄ -

e φ

Cl HH -S (CH ₂ ) ₄ CO ₂ Na

φ e

Cl HH -N (CH ₃ ) ₃ Cl

Cl HH -OCH ₂ CH-CH ₂

»Φ

Cl HH

Cl HH -OCK ₂ CH-CH ₂

Cl HH -OCH ₂ CH (OH) CH ₂ OH

Cl H H -θΡ / J

Cl HH -Ο- ( Π

ο ©

Cl HH -0-P ^ ^Φ

X) CH ₂ CH ₂ N (CH ₃ ) 3

List E (continued)

Cl

CH ₃ OCH ₃

 4

Cl

Cl

Cl

Cl

Cl

Cl

Cl

c \

CH ₃

CH ₃

H is -OCH (CH ₃ ) 2

H is -OCH (CH ₃ ) 2

H is -OCH (CH ₃ ) ₂

-OCH (CH ₃ ) ₂

-OCH (CH ₃ ) ₂

CH ₃ -OCH (CH ₃ ) ₂

-CH ₂ C = CH-OCH (CH ₃ ) ₂

-OCH ₂ CO ₂

List E (continued)

R R R R

Cl HH -SCH (CH ₃ ) ₂

H Cl HH -OCH ₂ CsCH

Cl H

H CJ HH -OCH ₂ CO ₂ CH (CH ₃ )

List F

OO

Cl

-OCH (CH)

0 0

Cl

-OCH CO

O O

Cl F ι

-SCH (CH> 3

O O

Cl

-OCH C = C-H

O O Ci H

-OCH (CH) _

O O Cl H

-OCH CO

O O Cl H

H . -SCH (CH

SS

Cl

-OCH (CH)

S S

Cl

-OCH CO

S S

Cl

-SCH (CH )

SS Cl H

-OCH (CH)

List F (continued)

A A '

J ₁ -

J, - J ₃ -

S S

Cl

Cl H

-OCH CO

0 0

Il

-OCCH.

Cl H

0 0

O Il

--OCOCH.

Cl

-OCH (CH ₃ )

0 0

-OCH F

Cl H

0 0 -OCH CH = CH F

2

Cl

0 0 -OCH C = C-H F

Cl

0 0

NH

Cl

0 0 -N (CH ₃ ) ₂

Cl

0 0

-SCH F

Cl H

0 0

-SCH ₃ F Cl

0 0

-SCH F Cl H

List F (Foreword)

A A '

J ₁ - J ₂ - J ₃ _ J ₄ .

0 0 -SH

HH-OCH (CH ₃ )

0 0 -OH

Cl H

H -OCH (CH)

0 0 -SO ₂ CH ₃ F

Cl H

H -OCH (CH)

0 0 -SOCH F

Cl H

H -OCH (ChT)

OS Cl

Cl H

H -OCH (CH ₃

0 S Cl

Cl H

H-OCH CO

-O

SS -SCH ₃ F

Cl H

H -OCH (CH ₃ )

S S-F

S S-F

H -SCH (OO

OO Cl

Cl CH.

H -OCH (CH )

OO Cl

Cl CH

CH-OCH (CH )

OO Cl

H -OCH (CH )

OO Cl

synthesis

The compounds contained in the compositions of the invention can be prepared by any one of several ways, depending on the particular heterocycle desired as Z. The following procedures illustrate the synthetic routes for the compounds.

The substances containing a 3,4,5,6-tetrahydrophthalimide ring system as Z are prepared by condensation of an appropriately substituted aniline (hereinafter simply referred to as "the aniline") with a substituted or unsubstituted cyclohexene-1,2- dicarboxylic anhydride, according to the equation:

The above reaction is carried out in the absence of a solvent or in a solvent such as acetic acid, methanol, toluene or dioxane at a temperature of 60 to 200 ^° C. When neutral solvents are used in the above-mentioned reaction, it is preferable to use a catalytic amount of a strong acid such as p-toluenesulfonic acid and to remove the water as it is produced by azeotropic distillation.

An alternative route to the N-phenyltetrahydrophthalimides of the invention is by the following scheme

stated:

(CF, SO,), 0 base

C-OSO ₂ CF,

base

In the above scheme, an aminobenzyl alcohol can be reacted with a cyclohexene-1,2-dicarboxylic anhydride as described above. The resulting product can be reacted with trifluoromethanesulfonic anhydride in the presence of a non-nucleophilic proton acceptor (such as pyridine, 2,6-lutidine or 2,6-di-tert-butylpyridine) to yield a highly reactive benzyl triflate (benzyl trifluoromethanesulfonate). The preferred solvent for forming the triflate is metlyl chloride or chloroform and the reaction should be carried out at ice bath temperature. The triflate should not be isolated but reacted with a nucleophilic compound Y while in solution. This latter reaction can be carried out in an ice bath, which can then warm to room temperature. The base used in this step may be the same as that used in the triflate-forming reaction. In the last step of the above reaction scheme, it is important that the benzyl triflate solution is dropwise added dropwise to the nucleophilic reagent HY in solution. The reverse addition leads to very low yields of the desired product. The N-phenyltetrahydrophthalimide process described above is particularly suitable for the synthesis of compounds containing Y groups which would not survive the acidic conditions required for condensation with a cyclohexene-1,2-dicarboxylic anhydride.

The Imidazolidindione can be prepared by reacting an isocyanate with Ethylpipecolinat and then - where necessary, to promote the cyclization - by treatment with an aqueous or alcoholic basic solution according to the following scheme:

Y-C

NH-C

CO ₂ Et

The reaction with the isocyanate can be carried out in any inert organic solvent, ζ. 8. dichloromethane, ethyl ether, toluene or the like, at a temperature of 20 to 125 ^° C. The bases which can be used for the cyclization include both inorganic bases such as sodium hydride or sodium hydroxide and organic bases such as triethylamine. The cyclization may be carried out in a variety of organic solvents such as ethanol, dichloromethane or toluene at a temperature of 20 to 100 ° C. Compounds in which Z is a urazole ring can be prepared according to the following reaction scheme:

H ₁ NNHCO ₂ Et

Y-C

R ₄

NH-C-NHNHCO ₂ Et

base

Br (CH ₄ UBr base

The Carboxylimidazol can be prepared by reaction of the aniline with carbonylbisimidazole in an inert organ Sichen solvent such as dichloromethane, ethyl ether or toluene at 20 to 100 ⁰ C. Bases which can be used for the cyclization of the reaction product from the Carboxylimidazol with ethyl carbamate, sodium hydride include and Sodium alkoxides in alcoholic or hydrocarbon solvents at 20 to 150 ° C. Bases which can be used for the conversion of the cyclized product to the urazole include alkali carbonates, sodium hydride or sodium alkoxides in solvents such as acetone, toluene, dimethylformamide and the like at temperatures of 20 to 150 ° C. The quinazolinones can be prepared as follows:

[H]

HC (OEt)

EtOH

The condensation of a nitrobenzoyl chloride with the aniline may be carried out in the presence of a proton acceptor such as triethylamine, potassium carbonate or the like at a temperature of -10 ⁰ C to +75 ⁰ C in an inert organic solvent such as carbon tetrachloride, dichloromethane or toluene. Reduction of the intermediate nitroamide can be accomplished by typical catalytic hydrogenation techniques, eg, over 5% Pt / C in an inert solvent such as ethanol, dichloromethane or acetic acid, or by chemical reduction methods such as refluxing the nitroamide in ethanol with one equivalent of stannous chloride. chloride. Cyclization of the quinazolinone can be accomplished by heating the amidoaniline with an orthoester such as triethyl orthoformate and distilling off the resulting alcohol. The temperature of the latter reaction is in the range of 100 to 200 ^° C. The imidazolinediones are prepared according to the following reaction scheme:

CHjNHCH ₁ CN

^ CH ₂ CN

The urea compound can be prepared by reacting either the isocyanate or imidazoyl derivative shown with methylaminoacetonitrile in an inert solvent (methylene chloride, toluene, chloroform, etc.) at room temperature. The cyclization of the urea compound to the imidazolidinedione can be accomplished by heating the urea compound in an aqueous acid solution in the presence of an inert organic solvent such as aqueous hydrochloric acid and toluene. The imidazolidinedione can be halogenated on the C ₄ -AtOm by heating under reflux in an inert organic solvent such as carbon tetrachloride with N-bromosuccinimide. The halogen can be easily replaced by a variety of nucleophilic groups such as alcohols, thiols and amines to obtain the desired product. The replacement reaction can be carried out in a variety of inert organic solvents such as acetone, dichloromethane, toluene and the like at a temperature of 0 to 100 ^° C. Higher yields can be achieved in the displacement reaction by adding silica gel to the reaction mixture. The 1,2,4-thiadiazolidine-1,1,3-triones can be prepared as follows:

CICH ₁ SO ₁ NHCH ₁

ti NH-C-N

SO ₂ CH ₂ Cl

The urea compound can be obtained by reacting either the isocyanate or the imidazoyl derivative of aniline with N-methylchloromethylsulfonamide. This reaction is carried out at 0 to 10O ⁰ C in an inert solvent such as dichloromethane, toluene or chloroform. The chloromethylsulfonylurea that forms can then be cyclized to the desired product by treating the urea compound with a base in an inert solvent. Suitable bases include organic bases such as pyridine or triethylamine or inorganic bases such as potassium carbonate. Suitable solvents for the cyclization include dichloromethane, toluene, ethers and the like

DIEA ¹ -Tetrahydroisophthalimide can be prepared as follows:

 QQ

The Tetrahydrophthalaminsäure can be prepared by reaction of the aniline in an inert solvent (benzene, toluene, dichloromethane, or the like) mit3,4,5,6-tetrahydrophthalic anhydride at a temperature in the range of 25 to 100 ⁰ C. The Tetrahydrophthalaminsäure obtained can be converted to demTetrahydrophthalimid are prepared by treatment with a dehydrating agent such as dicyclohexylcarbodiimide at a temperature of 25 to 75 ° C and in an inert solvent such as benzene, toluene, dichloromethane or the like.

The α-chlorophthalimide ketals and α-chlorohexahydrophthalimides can be obtained according to the following reaction scheme:

HQAc

Ri

The hexahydrophthalimide can be prepared by heating a mixture of the aniline and 1,2-cyclohexanedicarboxylic anhydride in a solvent such as acetic or propionic acid. The a-chloro-ketalamide can be prepared by heating the hexahydrophthalimide with phosphorus pentachloride containing a catalytic amount of phosphorus oxychloride and then quenching the reaction mixture with an ice-cold solution of pyridine in an alcohol, ROH. The a-chlorohexahydrophthalimide can be prepared by heating the ketalamide in glacial acetic acid. The latter reaction must be carefully monitored by TLC (thin layer chromatography), as prolonged heating will result in the elimination of hydrogen chloride below Bilduna of TfitrahvdrnnhthalimiH.

The anilines used in the process are themselves new. A general procedure leading to anilines in which R ₃ = R ₄ = H is given in the following reaction scheme:

O ₁ N

O, N

CH ₂ OSO ₂ CF ₁

CH ₁ Y

The benzoic acids can be prepared by treating the corresponding toluene in glacial acetic acid containing a catalytic amount of cobalt acetate, manganese acetate, tertiary butyl peroxide and 48% hydrobromic acid with oxygen gas at 20.7 bar (300 psi) and 130 to 150 ° C in a pressure vessel , The benzoic acids can be nitrated in the m-position to the carboxyl group by adding them to a 1: 1 mixture of nitric acid and sulfuric acid at a temperature of 0 to 50 ° C. The resulting nitrobenzoic acids can be selectively reduced by treatment with diborane at 0 ° C in tetrahydrofuran. This gives excellent yields of the nitrobenzyl alcohols. The trifluoromethanesulfonate esters can be prepared by adding a solution of a benzyl alcohol and a non-nucleophilic proton acceptor (pyridine 2,6-lutidine or 2,6-di-tert-butylpyridine) to an ice-cold solution of trifluoromethanesulfonic anhydride in a non-nucleophilic solvent (methylene chloride, Chloroform, carbon tetrachloride or the like). The trifluoromethanesulfonate esters are extremely reactive compounds. They should therefore not be isolated or stored but should be reacted immediately in solution with any of a variety of nucleophilic reagents HY as defined above to yield the Y-substituted nitro compounds. The latter substances can be reduced to the desired aniline product by catalytic or chemical reduction procedures. In the case of the particularly unstable Y-substituted nitro compounds, a particularly mild and effective method of reducing the aniline is to heat the nitro compound of an ethanolic tin-II chloride solution under reflux.

The trifluoromethanesulfonate esters used in the above-mentioned synthesis process for producing the anilines react little or not with carbon nucleophiles. Consequently, the anilines used, in which Y is bound to the C ₅ methylene group via a carbon-carbon bond, prepared according to the following reaction scheme;

wherein X is halogen and R ₁ and R _{2 have} the meaning given above.

The halogenation of the methyl group in the side chain can be carried out with a variety of known radical halogenating agents. An example of a reagent suitable for this purpose is N-bromosuccinimide with a catalytic group of a radical initiator, such as dibenzoyl peroxide. Solvents for this purpose include a variety of halogenated hydrocarbons, eg. For example, carbon tetrachloride, and the reaction is carried out under autogenous conditions in the temperature range of 50 to 150 ° C. The second step in the above reaction sequence, d. H. the replacement of halogen by cyanide in the benzyl function can be carried out by heating the benzyl halide with alkali cyanides such as potassium cyanide in any of various inert solvents such as ethanol, benzene, toluene or the like. A particularly preferred process for the preparation of benzyl cyanide is by heating an aqueous solution of sodium cyanide containing a phase transfer agent, e.g. B.Tricaprylmethylammonium chloride, with a toluene solution of the benzyl halide under reflux. The resulting benzyl cyanide can be nitrided by treatment with excess fuming nitric acid. The nitration is carried out in the temperature range of 15 to 75 ° C. The nitrobenzyl cyanides are reduced to the desired anilines using a catalytic or chemical reduction process. The β-benzyl cyanides occurring as intermediates in the second step of the above reaction sequence are themselves valuable intermediates for other compounds, as shown below:

C-CX

Thus, one or both of the benzylic hydrogens can be replaced by treating the benzyl cyanide with a strong base and then with an alkylating agent R ₃ -X where X is bromo, chloro, a sulfonate ester or the like. This process can be repeated by adding a second equivalent of a strong base and the alkylating agent R4-X. Examples of strong bases that can be used for this reaction include alkali metal hydrides, eg, sodium hydride and alkali metal salts of amines, e.g. B. lithium diisopropylamide. The alkylated benzyl cyanides can be nitrated in exactly the same manner as described above for the benzyl cyanides. Treatment of the resulting nitrobenzyl cyanides with aqueous mineral acids effects the hydrolysis of the cyano group to a functional carboxylic acid group from which other derivatives can be prepared in various known ways. These conversions are given below.

wherein Q = alkoxy, amine, substituted amine, etc.

A preferred group of anilines can be prepared using 2-chloro-4-fluorotoluene, a compound that is commercially available. This preferred group has the general formula:

in which Y has the meaning given above. The synthesis can be specifically explained for 2-fluoro-4-chloro-5-isopropoxymethyleneaniline. It works according to the following scheme:

chlorination

ENT,

H ₁ SO.

) -0H

CH]

The chlorination of 2-chloro-4-fluorotoluene is carried out under conditions in which a chlorine radical is formed to give 2-chloro-4-fluorobenzyl chloride. Selective nitration at the 5-position to form 2-chloro-4-fluoro-5-nitrobenzyl chloride is carried out using an aqueous nitration mixture of nitric acid and sulfuric acid. The conversion of 2-chloro-4-fluoro-5-nitrobenzyl chloride to isopropyl ^ -chloro-fluoro-S-nitrobenzyl ether is carried out by heating the benzyl chloride in the presence of isopropyl alcohol under pressure. It will be understood by those skilled in the art that the conversion of the nitrobenzyl chloride to the nitrobenzyl ether can also be achieved under various acid catalyzed conditions, such as. But not exclusively by the use of zinc chloride, p-toluenesulfonic acid, aluminum trichloride and silver salts. Subsequent hydrogenation of the nitrobenzyl ether using Pt / C or Raney nickel of the catalyst yields 2-fluoro-4-chloro-5-isopropoxymethylaniline. The aniline is condensed without isolation with 3,4,5,6-tetrahydrophthalic anhydride. This condensation reaction is carried out in the absence of a solvent or in a solvent such as acetic acid, methanol, toluene or dioxane at a temperature of 60 to 200 ° C. If desired, a catalytic amount of acid, e.g. B. p-toluenesulfonic acid are added to accelerate the condensation.

Although the above-mentioned group of anilines and corresponding 5-substituted methylenanilides have been explained in the case where Y is an isopropoxy group, corresponding to the use of isopropyl alcohol, HY, as reagent, this reaction scheme is generally applicable to nucleophilic reactants HY, including amines, alcohols , Mercaptans, etc.

In addition, various of the steps used to prepare intermediates for forming the above-identified anilines are novel and generally applicable. The nitration of 2-chloro-4-fluorobenzyl chloride is an example of a specific nitration, ie, the specific nitration in the C ₅ position, which can be generally used to prepare 2,4-dihalo-5-nitrobenzyl chlorides. The reaction is carried out by reacting a 2,4-dihalobenzyl chloride with an aqueous nitrating solution having a concentration of about 10 to about 50 weight percent nitric acid and a concentration of between about 20 and about 85 weight percent sulfuric acid at a temperature between about 15 ⁰ C and about 100 ° C. An amount of nitrating solution is used which provides at least a stoichiometric amount of nitric acid, that is, the reaction is carried out at a molar ratio of at least 1: 1 nitric acid: 2,4-dihalobenzyl chloride.

Also, the process of reacting a 2,4-dihalo-5-nitrobenzyl chloride with an alcohol as a nucleophilic reagent to form a 2,4-dihalo-5-nitrobenzyl ether exemplified by the reaction of 2-chloro-4-fluoro-5 -nitrobenzyl chloride with isopropanol, is new in that it can be carried out in the absence of an additional catalyst and still gives good yields. The alcohol is reacted in at least stoichiometric amount with the benzyl chloride at a temperature of 50 ⁰ C to 25O ⁰ C and a pressure of atmospheric pressure to 20,7bar (300 psi). A special case of this reaction occurs when the nucleophilic reagent employed is water, thereby allowing an economical process for the preparation of 2,4-dihalo-5-nitrobenzyl alcohols in good yield. Inert solvents, such as dioxane, toluene and the like, can be used as the reaction medium, although their use is not mandatory. In addition, the preparation of 2-chloro-4-fluoro-5-nitrobenzylamines can be achieved by a new reaction, as exemplified for the preparation of 2-chloro-4-fluoro-5-nitrobenzylmorpholine, as shown below:

NO-

NaOH

The nitration of 2-chloro-4-fluorobenzylmorpholine is an example of a specific nitration, ie, a specific nitration on the C ₅ -AtOm, which can be generally used for the preparation of 2,4-dihalo-5-nitrobenzylamines. The reaction is carried out by reacting a 2,4-Dihalogenbenzylamins with an aqueous Nitrierungslösung at a concentration of about 10 to 50wt .-% nitric acid and a concentration of between about 20 and about 85Gew .-% sulfuric acid, at a temperature between about -15 ⁰ C and about 100 ° C. An amount of nitrating solution is used which provides at least a stoichiometric amount of nitric acid and sulfuric acid, that is, the reaction is carried out at a molar ratio of at least 1: 1 of both nitric acid and sulfuric acid to the 2,4-dihalobenzylamine. The initially formed 2,4-dihalo-5-nitrobenzylamine sulfate can either be isolated or treated directly with a base such as sodium hydroxide, potassium hydroxide or the like to obtain the free 2,4-dihalo-5-nitrobenzylamine. Subsequent hydrogenation and coupling with 3,4,5,6-tetrahydrophthalic anhydride according to methods already described gives the desired 5-substituted Methylenanilide.

Many of the methylenanilide compounds of this invention can be conveniently prepared from a corresponding tetrahydrophthalimidobenzyl alcohol according to the following scheme:

CH ₂ OH

CH ₂ OH

The above-mentioned reaction steps can be carried out as described above. The Tetrahydrophthalimidobenzhylaikohol can be readily oxidized to the corresponding aldehyde, which in turn is useful as an intermediate for various compounds of the invention, in particular those in which R ₃ and R ₄ are not hydrogen. For example, below is shown how compounds where R ₃ = R ₄ = F can be prepared:

CH, 0H

CHO

The conversion of the starting benzyl alcohol to the intermediate benzaldehyde is carried out by adding trifluoroacetic anhydride to dimethyl sulfoxide in methylene chloride at the temperature of a dry ice-acetone bath (about -76 ° C) and then adding the benzyl alcohol and then triethylamine. The resulting aldehyde is converted to the desired fluorinated product by treatment with diethylaminosulfur trifluoride in methylene chloride at room temperature.

embodiments

The preparation examples given below illustrate further specific processes which are suitable for the preparation of the compounds contained in the agents according to the invention. The numbers given in parentheses after the title compound in each example are the same as those of the compound in Table III, in which physical properties and elemental analyzes are given.

Production Example 1 N- (2-fluoro-4-chloro-5-acetoxymethylenephenyl) -3,4,5,6-tetrahydrophthalimide (1)

A 3 L round bottom flask was fitted with a mechanical stirrer, thermometer and reflux condenser with N ₂ inlet. Into the flask, 130 g (0.82 mol) of potassium permanganate in 1 500 ml of water and 50 g (0.346 mol) of 2-chloro-4-fluorotoluene were added. The mixture was slowly heated to reflux and refluxed for 5 hours. The reflux condenser was replaced with a Liebig condenser and collected about 300 ml of distillate. The hot residue was filtered through celite, concentrated in vacuo and concentrated with 60 ml of conc. HCI acidified. The solution was cooled in an ice bath, the precipitate was filtered off by suction and washed with water. The solid was taken up in ether, dried over MgSO4 and the solvent removed. This gave 22.3 g (37%) of 2-chloro-4-fluorobenzoic acid as a white solid. NMR (d ₆ -acetone): δ 7.00-7.55 (m, 2H); 7.88-8.21 (d pair, 1H); 9.30 (s wide, 1 H).

A 500 ml round bottom flask was fitted with a mechanical stirrer, thermometer, reflux condenser with N ₂ inlet and dropping funnel. In the flask were 100ml conc. Sulfuric acid and cooled in an ice bath. The 2-chloro-4-fluorobenzoic acid (19.3 g, 0.111 mol) was added in portions. A nitrating acid mixture of 20 ml fuming nitric acid and 20 ml conc. Sulfuric acid was dropped under the surface while keeping the temperature at 0 to 5 ° C. After complete addition, the reaction mixture was stirred for 1 h at 5 ⁰ C and then allowed to warm to room temperature. The mixture was then heated at 50 ° C. for 1 h ² h. The reaction mixture was poured onto ice to give a white solid precipitate. This solid was filtered off with suction, taken up in ethyl acetate, dried over MgSO ₄ and the solvent removed. To give 20,3g (83%) of 2-chloro-4-fluoro-5-nitrobenzoic acid as a pale yellow solid, mp 183-185 ⁰ C. NMR (ds-acetone). Δ 7.72 (d, 1 H); 8.68 (d, 1H), 10.15 (s wide, 1H).

A 1-liter round bottom flask was equipped with magnetic stirrer, reflux condenser with N 2 inlet, thermometer and dropping funnel. To the flask was added 185 ml (0.90 mol) of 1M diborane in tetrahydrofuran. This was cooled using an ice bath to 0 ⁰ C and added dropwise a solution of 2-chloro-4-fluoro-5-nitrobenzoic acid indicated above in 200 ml of tetrahydrofuran. After complete addition, the reaction mixture for 1 ¹ / 2h was heated unterRückfluß. The mixture was then cooled in an ice bath and 50 ml 3 η HCl added dropwise. The reaction mixture was concentrated in vacuo and the residue was triturated with ether three times. The ether was washed twice with water, once with saturated NaHCO ₃ solution and once more with water and then dried over MgSC> 4 and the solvent removed leaving a yellow solid. This was washed with hexane to give 17.2 g (93%) of 2-chloro-4-fluoro-5-nitrobenzyl alcohol. NMR: (CDCl ₃ ): δ 3.10 (s wide, 1 H); 4.80 (s, 2H); 7.30 (d, 1H); 8.23 (d, 1H).

A 250-m round-bottomed flask was fitted with magnetic stirrer and reflux condenser with N ₂ inlet and 5.0 g (0.0243 mol) of the above-identified 2-chloro-4-fluoro-5-nitrobenzyl alcohol, 27.4 g (0.122 mol) stannous-II chloride dihydrate and 75 ml of absolute ethanol. The reaction mixture was heated to 70 ⁰ C for 2 h. The reaction mixture was concentrated under reduced pressure (vacuum) and poured onto ice. The pH of the mixture was adjusted to 7.5 with solid sodium bicarbonate and (the mixture) extracted with ethyl acetate. The ethyl acetate was washed twice with brine, dried over MgSO4 and the solvent removed. There remained 2.9 g (68%) of 2-chloro-4-fluoro-5-aminobenzyl alcohol as a white solid. NMR: (acetone-d ₆ ): δ4.35 (s, broad, 2H); 4.51 (s, 2H); 6.95 (d, 1H); 1.72 (d, 1H).

A 100 ml round bottom flask was fitted with a magnetic stir bar and reflux condenser with N ₂ inlet. Into the flask were added 2.9 g (0.0165 mol) of 2-chloro-4-fluoro-5-aminobenzyl alcohol, 2.5 g (0.0165 mol) of 3,4,5,6-tetrahydrophthalic anhydride and 25 ml of glacial acetic acid. The reaction mixture was heated to reflux for 12 hours, then poured onto ice and extracted with toluene. The toluene extract was washed twice with water, once with saturated sodium bicarbonate solution and again with water. The solution was dried over MgSO ₄ and the solvent removed leaving an orange oil. This was purified by flash chromatography over silica gel to give 2.9 g (50%) of N- (2-fluoro-4-chloro-5-acetoxy-methylene-phenyl) -3,4,5,6-tetrahydrophthalimide as a clear glassy one Product.

analysis % C %H % N calculated 58.04 4.30 3.98 found 57.54 4.57 3.80

Production Example 2

N- (2-fluoro-4-chloro-5-isopropoxymethylenphenyl) -3,4,5,6-tetrahydrophthalimide (2);

A 100 ml round bottom flask was fitted with a magnetic stir bar and drop funnel with N ₂ inlet. To the flask was added 25 ml of methylene chloride containing 4.12 g (0.0146 mol) of trifluoromethanesulfonic anhydride and cooled in an ice bath. A solution of 3.0 g (0.0146 mol) 2-chloro-4-fluoro-5-nitrobenzyl alcohol (prepared as indicated in Example 1) and 1.15 g (0.0146 mol) pyridine in 10 mL CH ₂ Cl _{2 was} added dropwise and the reaction mixture Stirred for 1 h in an ice bath. This mixture was through

filtered anhydrous sodium sulfate and used immediately as follows.

A 100 ml round bottom flask was equipped with magnetic stirrer and N ₂ inlet dropping funnel. To this flask was added 25 ml of CH ₂ Cl ₂ , 1.32 g (0.0220 mol) of isopropanol and 10 g of anhydrous potassium carbonate. The Trifluormethansulfonatester as prepared above was added dropwise and the reaction mixture stirred for 4 h at room temperature. The reaction mixture was poured into ice-water and extracted with CH ₂ Cl ₂ . The CH ₂ Cl ₂ was washed three times with water, dried over MgSO ₄ and the solvent removed. It left a viscous orange oil. The oil was purified by flash chromatography over silica gel using 90:10 hexane: ethyl acetate to give 2.4 g (66%) of isopropyl 2-chloro-4-fluoro-5-nitrobenzyl ether as a yellow oil. NMR (CDCl ₃ ): δ 1.23 (d, 6H); 3.48-4.00 (m, 1H); 4.52 (s, 2H); 7.28 (d, 1H); 8.25 (d,

In a pressure bottle were 2.4 g (0.0097 mol) of the above 2-chloro-4-fluoro-5-nitrobenzyl ether, 30 ml of glacial acetic acid and

0.25 g of 5% Pt / C and hydrogenated in a hydrogenation apparatus with 2.8 bar (40 psi) of hydrogen for 30 minutes. Thin layer chromatography analysis showed complete disappearance of the nitro compound. The hydrogenated mixture was filtered through celite to remove the catalyst, and the filtrate, containing 2-fluoro-4-chloro-5-isopropoxymethyleneaniline, was placed in a 100 mL round bottom flask equipped with magnetic stirrer and N ₂ inlet reflux condenser was provided. To the filtrate was added 1.77 g (0.0116 mol) of 3,4,5,6-tetrahydrophthalimide, and the mixture was refluxed overnight. The reaction mixture was poured onto ice and extracted with toluene. The toluene was washed twice with water, twice with saturated NaHCO ₃ solution and again with water. After drying the toluene over anhydrous MgSCU, the solvent was removed and an orange oil remained. This was purified by flash chromatography on silica gel using 90:10 hexane: ethyl acetate to give 1.90 g (56%) of N- (2-fluoro-4-chloro-5-isopropoxymethylenephenyl) -3,4,5,6-tetrahydrophthalimide as a white solid, m.p. 100-1.03 ⁰ C.

Analysis% C% H% N

calculated 61.45 5.44 3.98

found . 61.89 5.67 3.75

Production Example 3

N- (2-Fluoro-4-chloro-5-carbomethoxymethylthiomethylphenyl) -3,4,5,6-tetrahydrophthalimide (4) The trifluoromethanesulfonate ester of 2-chloro-4-fluoro-5-nitrobenzyl alcohol was prepared as a solution in methylene chloride using 3.5 g (0.0175 mol) of the alcohol and using the method described in Example 2. A 100 ml round bottomed flask was equipped with magnetic stir bar and drop funnel with N ₂ inlet. In this flask, 10 ml CH ₂ CI ₂ containing 1.99 g (0,0187mol) methyl thioglycolate and 10 g anhydrous K2CO3 given. The CH ₂ Cl ₂ solution of the trifluoromethanesulfonate ester was added dropwise to the flask and the reaction mixture was stirred for 1 h at room temperature, then poured onto ice and extracted with CH ₂ Cl ₂ . The CH ₂ Cl ₂ was washed three times with water, dried over MgSO ₄ and the solvent removed to leave a tan liquid. This was purified by flash chromatography on silica gel to give 2.4 g (48 g) of methyl 2-chloro-4-fluoro-5-nitrobenzyl thioglycolate as a yellow solid. NMR (CDCl ₃ ): δ 3.20 (s, 1H); 3.80 (s, 6H); 4.02 (s, 2H); (d, 1H); 8.25 (d, 1H).

The methyl thioglycolate product was taken up in acetic acid and reduced catalytically using 5% Pt / C as described in Example 2. The resulting acetic acid solution of methyl 1-chloro-fluoro-o-aminobenzyithioglycolate was refluxed for 12 hours with 1.50 g (0.0098 mol) of 3,4,5,6-tetrahydrophthalimide and worked up as described in Example 2 to an orange oil. This oil was purified by flash chromatography on silica gel using 70:30 hexane: ethyl acetate to give 1.45 g (44%) of N- (2-fluoro-4-chloro-5-carbomethoxymethylthiomethylphenyl) -3,4,5,6- tetrahydrophthalimide as a yellow oil.

analysis % C %H % N calculated 54.34 4.31 3.52 found 53.81 4.43 3.45

Production Example 4

N- (4-chloro-5-iso-propoxymethylphenyl) -3,4,5,6-tetrahydrophthalimide (17)

Into a pressure bottle, 140 ml of glacial acetic acid, 20.0 g (0.107 mol) of 2-chloro-5-nitrobenzyl alcohol and 2.0 g of 5% Pt / C were added. The mixture was shaken for 4 h under a hydrogen pressure of 2.8 bar (40 psi) in a hydrogenation apparatus. Thin layer chromatography showed that the reduction of the aniline was complete. The catalyst was filtered through celite and the acetic acid evaporated in vacuo to leave a yellow solid. This solid was washed thoroughly with ethyl ether to give 14.6 g (86%) of 2-chloro-5-aminobenzyl alcohol as a white solid.

A 500 ml round bottom flask was fitted with a magnetic stir bar, a Dean-Stark trap with reflux condenser, and a N ₂ inlet. To the flask were added 14.5 g (0.092 mol) of 2-chloro-5-aminobenzyl alcohol, 15.4 g (0.101 mol) of 3,4,5,6-tetrahydrophthalic anhydride and 50 mg of p-toluenesulfonic acid. 150 ml of toluene were added to this mixture and the resulting mixture was heated under azeotropic removal of the resulting water via the Dean-Stark-Faile under reflux. After refluxing for 6 hours, the reaction mixture was cooled to room temperature, washed twice with water, dried over MgSO ₄ and the solvent removed to leave an orange solid. This was washed thoroughly with ethyl ether to give 21.6 g (80%) of N- (4-chloro-5-hydroxymethylphenyl) -3,4,5,6-tetrahydrophthalimide as a light yellow solid, m.p. 121-124 ° C. NMR (CDCl ₃ ): δ 1.50-2.10 (m, 4H); 2.10-268 (m, 4H); 3.00 (s, wide, 1H); 4.78 (s, 2H); 7.05-7.70 (m, 3H).

A 250 ml round bottom flask was fitted with magnetic stirrer and N ₂ inlet funnel. 25 ml of CH ₂ Cl ₂ and 4.84 g (0.0171 mol) of trifluoromethanesulfonic anhydride were added to the flask and cooled in an ice bath. A mixture of 5.0 g (0.0171 mol) of N- (4-chloro-5-hydroxymethylphenyl) -3,4,5,6-tetrahydrophthalimide and 1.36 g (0.0171 mol) of pyridine in 25 mL of CH ₂ Cl ₂ was added dropwise to the trifluoromethanesulfonic anhydride solution. After stirring at 0 ° C for 1 hour, the reaction mixture was filtered through anhydrous sodium sulfate and immediately used as follows.

Into a 250 ml round bottom flask equipped with magnetic stirrer and N ₂ inlet funnel were added 10 g of anhydrous K ₂ CO ₃ , 20 ml of CH ₂ Cl ₂ and 1.5 g (0.0257 mol) of 2-propanol. DieCH ₂ CI ₂ solution desTrifluormethylsulfonatesters of N- (4-chloro-5-hydroxymethylphenyl) -3,4,5,6-tetrahydrpphthalimid, which had been prepared above was added dropwise to the isopropanol K ₂ CO ₃ mixture. After stirring overnight at room temperature, the reaction mixture was washed three times with water, dried over MgSO ₄ and the solvent removed leaving a yellow solid. This solid was purified by flash chromatography on silica gel using 90:10 hexane: ethyl acetate to give 2.5 g (44%) of N- (4-chloro-5-isopropoxymethylphenyl) -3,4,5,6-tetrahydrophthalimide as a white solid, mp. 120-121 ⁰ C.

analysis % C %H % N calculated 64.77 6.04 4.19 found 64.89 6.03 4.06

Production Example 5

N- (2-Fluoro-4-chloro-5-glycidoxymethylphenyl) -3,4,5,6-tetrahydrophthalimide (47) Into a 1 liter stirred flask equipped with magnetic stirrer, Dean-Stark trap and N-reflux condenser. 18.7 g (0.107 mol) of 2-chloro-4-fluoro-5-aminobenzyl alcohol (see Example 1 for the preparation of the intermediate), 17.8 g (0.117 mol) of 3,4,5,6 Tetrahydrophthalic anhydride and 200 mg of p-toluenesulfonic acid in 300 ml of toluene. The mixture was refluxed overnight with simultaneous azeotropic removal of the water formed in the reaction. Removal of the solvent left a tan oil. This oil was purified by flash chromatography on silica gel using 60:40 hexane: ethyl acetate to give 22.1 g (67%) of N- (2-fluoro-4-chloro-5-hydroxymethylphenyl) -3,4,5,6 tetrahydrophthalimide as a white solid. NMR (CDCl ₃ ): δ 1.48-202 (m, 4H); 2.02-2.60 (m, 4H); 2.98 (s, wide, 1H); 4.65 (s, 2H); 7.05-7.50 (m, 2H).

Into a 100 ml round bottomed flask equipped with magnetic stirrer and N ₂ inlet funnel was placed 10 ml of CH ₂ Cl ₂ and 2.73 g (0.0097 mol) trifluoromethanesulfonic anhydride and cooled in an ice bath. 0.097 mol) of N- (2-fluoro-4-chloro-5-hydroxymethylphenyl) -3,4,5,6-tetrahydrophthalimide and T, 04g (O, 0097mol2,6-lutidine in 15 ml of CH ₂ Cl ₂ was added dropwise was stirred for 1 h at 0 ° C, then filtered through anhydrous sodium sulfate and used immediately in the next step as follows.

A 100 ml flask was fitted with a magnetic stirrer and N ₂ inlet funnel. To the flask was added 10 ml of CH ₂ Cl ₂ , 2.87 g (0.0387 mol) of glycidol and 4.0 ml of 2,6-lutidine. The trifluoromethylsulfonate ester prepared as described above was added dropwise to the glycidol solution in an ice bath. The reaction mixture was stirred for 2 h at room temperature, then washed with water, with 5% HCl and again with water. The solution was dried over MgSO4 and the solvent. removed in vacuo to give an orange oil. This oil was purified by flash chromatography on silica gel using 60:40 hexane: ethyl acetate to give 1.40 g (39%) of N- (2-fluoro-4-chloro-5-glycidoxymethylphenyl) -3,4,5,6- tetrahydrophthalimide as a viscous oil.

analysis % C %H % N calculated 59.10 4.68 3.83 found 58.78 5.01 3.79

Production Example 6

N- [2-fluoro-4-chloro-5- (2,2-dimethyl-1,3-dioxolane-4-methoxymethyl) -phenyl] -3,4,5,6-tetrahydrophthalimide (65) Using the method described in Example 5, the trifluoromethylsulfonate ester was prepared from 3.0 g (0.0097 mol) of N- (2-fluoro-4-chloro-5-hydroxymethylphenyl) -3,4,5,6-tetrahydrophthalimide in 30 mL of CH ₂ Cl ₂ . Into a 100 ml round bottom flask equipped with magnetic stirrer and reflux condenser with N ₂ inlet was added 10 ml of CH ₂ Cl ₂ containing 1.56 g (0.0145 mol) of 2,6-lutidine and 1.28 g (0.0097 mol) of 2,2-dimethyl-1,3-dioxolane-4-methanol and cooled in an ice bath. To this solution was added the trifluoromethanesulfonate ester prepared as above. The reaction mixture was stirred overnight at room temperature, then washed with 5% HCl and twice with water and dried over MgSO ₄ . Removal of the solvent left an orange oil which was purified by flash chromatography (column) using 60:40 hexane: ethyl acetate. This gave 1.55 g (38%) of N- [2-fluoro-4-chloro-5- (2,2-dimethyl-1,3-dioxolan-4-methoxymethyl) phenyl] -3,4,5,6- tetrahydrophthalimide as a pale yellow oil.

analysis % C %H % N calculated 57.50 5.47 3.30 found 57.26 5.28 3.45

Production Example 7

N- [2-fluoro-4-chloro-5- (1,2,5,6-diisopropylidene-D-glucose-O-methyl) -phenyl] -3,4,5,6-tetrahydrophthalimide (63) A 100 -ml round bottom flask was equipped with magnetic stirrer and dropping funnel with N ₂ inlet. Into the flask, 3.19 g (0.0113 mol) of trifluoromethylsulfonic anhydride and 15 ml of CH ₂ Cl _{2 were} added and cooled in an ice bath. A solution of 3.5 g (0.0113 mol) of N- (2-fluoro-4-chloro-5-hydroxymethylphenyl) -3,4,5,6-tetrahydrophthalimide and 2.16 g (0.0113 mol) of 2,6-di tert -butylpyridine in 40 ml CH ₂ Cl ₂ was added dropwise. The mixture was stirred 1 h at 0 ⁰ C, filtered through anhydrous sodium sulfate and used immediately in the below-described step.

A 100 ml round bottom flask was fitted with a magnetic stirrer and N ₂ inlet funnel. Into the flask were added 4.41 g (0.0170 mol) of 1,2,5,6-diisopropylidene-D-glucose and 2.39 g (0.0124 mol) of 2,6-di-tert-butylpyridine in 10 ml of CH ₂ Cl ₂ given. The Trifluormethylsulfonatester as prepared above was added dropwise and the reaction mixture was stirred overnight at room temperature. The reaction mixture was washed twice with water, dried over MgSO ₄ and the solvent removed leaving an orange oil. This oil was purified by flash chromatography (column) over silica gel using 80:20 hexane: ethyl acetate to give 4.4 g (71%) of N- [2-fluoro-4-chloro-5- (1,2,5,6 -diisopropylidene-D-glucose-O-methyl) phenyl] -3,4,5,6-tetrahydrophthalamide, m.p. 68-72 ° C.

analysis % C %H % N calculated 58.75 5.66 2.54 found 58.76 5.53 3.92

Production Example 8

N - ^ - fluoro-chloro-S-cyclopentyloxycarbonylmethyloxymethyl-phenyl-SAS-tetrahydrohthalimidi-Sg) To a 100 ml round bottomed flask equipped with magnetic stirrer and N ₂ inlet funnel was added 20 ml of CH ₂ Cl ₂ and 1 , Added 96 g (0.00694 mol) of trifluoromethylsulfonic anhydride. The mixture was cooled to ⁰ ° C. and a solution of 2.15 g (0.00694 mol) of N- (2-fluoro-4-chloro-5-hydroxymethylphenyl) -3,4,5,6-tetrahydrophthalimide and 0.74 g ( 0.00694 mol) of 2,6-dimethylpyridine in 15 ml of CH ₂ Cl _{2 was} added dropwise. The reaction mixture was stirred for 1 h at 0 ° C, filtered through anhydrous sodium sulfate and immediately used as follows.

Into a 100 ml round bottom flask, equipped with magnetic stirrer and N ₂ inlet funnel, was 4.81 g anhydrous

K ₂ CO ₃ and 20 ml CH ₂ CI ₂ containing 1.50 g (0,104mol) Cyclopentylglykolat. The CH ₂ Cl ₂ solution of the trifluoromethylsulfonate ester as prepared above was added dropwise, and the mixture was stirred at room temperature for 12 hours. The mixture was washed three times with water, dried over MgSO ₄ and the solvent removed to leave an oil. This oil was purified by flash chromatography on silica gel using 75:25 hexane: ethyl acetate to give 1.37 g (45%) of N- [2-fluoro-4-chloro-5- (cyclopentyloxycarbonylmethyloxomethyl) phenyl] -3.4, 5,6-tetrahydrophthalimide as a white solid, m.p. 84-86 ° C.

analysis % C %H % N calculated 60.62 5.32 3.23 found 60.70 5.36 3.32

Production Example 9

N- [2-Fluoro-4-chloro-5- (N-methylaminocarbonyloxymethyl) -phenyl] -3,4,5,6-tetrahydrophthalimide (34) Into a 250 ml pressure flask fitted with magnetic stirrer were added 1 , 9g (0.00613mol) of N- (2-fluoro-4-chloro-5-hydroxymethyl) phenyl-3,4,5,6-tetrahydrophthalimide (see Example 5), 50ml CH ₂ Cl ₂ , 0.42g (0 The flask was sealed and stirred at room temperature for two days The solvent was removed under reduced pressure and the residue was purified by flash chromatography on silica gel using 50:50 Hexane: ethyl acetate to give 1.25 g (56%) of N- [2-fluoro-4-chloro-5- (N-methylaminocarbonyloxymethyl) phenyl] -3,4,5,6-tetrahydrophthalimide as a white solid, m.p. 34 -41 ⁰ C.

analysis % C %H % N calculated 55.67 4.40 7.64 found 54.81 4.48 7.40

Production Example 10

N- (2-Fluoro-4-chloro-5-cyclopentyloxycarbonyloxymethyl) phenyl-3,4,5,6-tetrahydrophthalimide (35) Into a 50 ml round bottom flask equipped with magnetic stirrer and N ₂ inlet funnel, were 1.22 g (0.00394 mol) of N- (2-fluoro-4-chloro-5-hydroxymethyl) phenyl-3,4,5,6-tetrahydrophthalimide (see Example 5) and 20 ml of CH ₂ Cl ₂ containing 0, 60g (0.0059mol) of triethylamine. The mixture was cooled in an ice bath and 0.58 g (0.00394 mol) of cyclopentyloxycarbonyl chloride (prepared from phosgene and cyclopentanone in 5 ml of CH ₂ Cl ₂ added dropwise.) The reaction mixture was stirred at room temperature for two days The solvent was removed under reduced pressure and the residue was passed through Purified via silica gel using 75:25 hexane: ethyl acetate to give 0.67 g (40%) of N- (2-fluoro-4-chloro-5-cyclopentyloxycarbonyloxymethyl) phenyl-3,4,5,6-tetrahydrophthalimide as an oil ,

Analysis% C% H% N

calculated 59.79 5.02 3.32

found 58.87 5.08 3.56

Production Example 11

N- (2-Fluoro-4-chloro-5-tetrahydropyran-2-oxymethyl) phenyl-3,4,5,6-tetrahydrophthalimide (7) Into a 100 ml round bottomed flask equipped with magnetic stirrer and N ₂ inlet 1.5 g (0.00484 mol) of N- (2-fluoro-4-chloro-5-hydroxymethyl) phenyl-3,4,5,6-tetrahydrophthalimide (see Example 5), 0.60 g (0.005 mol ) Dihydropyran, 100 mg of p-toluenesulfonic acid and 20 ml of ToJuol. The reaction mixture was stirred for two days at room temperature. The solvent was removed in vacuo. It left behind 2.0g of a viscous tan oil. This oil was purified by silica gel low pressure liquid chromatography to give 1.3 g (71%) of N- (2-fluoro-4-chloro-5-tetrahydropyran-2-oxymethyl) phenyl-3,4,5,6-tetrahydrophthalimide colorless glassy product.

analysis % C % H % N calculated 60.99 5.37 3.56 found 60.40 5.53 3.52

Production Example 12

N- (2-fluoro-4-chloro-5-difluoromethyl) -3,4,5,6-tetrahydrophthalimide (52)

Into a 100 ml round bottom flask fitted with magnetic stirrer, N ₂ inlet and septum (inlet), 1.0 g (0.00325 mol) of 2-chloro-4-fluoro-5- (3,4,5, 6-tetrahydrophthalimide) benzaldehyde and 50 ml of CH ₂ Cl ₂ . The mixture was cooled in an ice bath and 0.80 ml (1.06 g, 0.0065 mol) of diethylaminosulfur trifluoride added via syringe. The reaction mixture was allowed to warm slowly to room temperature and stirred for 20h. Thin-layer chromatography of the reaction mixture showed that no aldehyde was present. The mixture was washed once with brine, dried over MgSO ₄ and the solvent evaporated to leave a thick brown oil. This oil was chromatographed over silica gel with CH ₂ Cl _{2 to} give 1.0 g (93%) of N- (2-fluoro-4-chloro-5-difluoromethyl) phenyl-3,4,5,6-tetrahydrophthalimide as a pale yellow solid, Mp 84-89 ⁰ C.

analysis % C %H % N % F calculated 54.65 3.37 4.25 17.29 found 54.47 3.50 - 16.56

Production Example 13

N- [2-fluoro-4-chloro-5- (2,5-dimethylbenzyl) -phenyl] -3,4,5,6-tetrahydrophthalimide (57) Into a 100 ml round bottom flask equipped with magnetic stirrer and dropping funnel with N ₂ inlet, 0.8 ml (1.3 g, 0.00484 mol) of N- (2-fluoro-4-chloro-5-hydroxymethyl) phenyl-3,4,5,6-tetrahydrophthalimide and 20 ml of p Given -xylene. The mixture

was cooled in an ice bath and 0.52 g (0.00484 mol) of 2,6-lutidine in 2 ml of p-xylene was added via the dropping funnel. The reaction mixture was allowed to come to room temperature. Thin layer chromatography showed that no benzyl alcohol used as the starting material was left. The reaction mixture was poured into ice-water and extracted with CH ₂ Cl ₂ . The CH ₂ Cl ₂ extracts were washed with water, dried over MgSO ₄ and the solvent removed under reduced pressure. The residue was taken up in hot hexane. Upon cooling, an oil separated and the hexane was decanted from the oil. The residual oil was purified by low pressure liquid chromatography on silica gel using CH ₂ Cl _{2 to give} 0.64 g (33%) of N- [2-fluoro-4-chloro-5- (2,5-dimethylbenzyl) -phenyl ] -3,4,5,6-tetrahydrophthalimide as a viscous oil.

Production Example 14

N- [2-fluoro-4-chloro-5- (n-butylthiomethyl) phenyl] -3,4,5,6-tetrahydrophthalimide (31)

Into a 100 ml round bottom flask equipped with magnetic stirrer and N ₂ inlet dropping funnel was placed 10 ml of CH ₂ Cl ₂ containing 4.0 g (0.0145 mol) of trifluoromethylsulfonic anhydride and cooled in an ice bath. A solution of 1.56 g (0.0145 mol) of 2,6-lutidine and 4.3 g (0.0139 mol) of N- (2-fluoro-4-chloro-5-hydroxymethyl) phenyl-3,4,5,6- tetrahydrophthalimide in 30 ml of CH ₂ Cl ₂ was added dropwise to the trifluoromethylsulfonic anhydride solution. After complete addition, the mixture was stirred in an ice bath for 1.5 h, then filtered through anhydrous sodium sulfate into a flask containing 5.1 g (0.0555 mol) butanethiol, 100 ml CH ₂ Cl ₂ and 9.7 g (0.070 mol) anhydrous K ₂ CO ₃ contained. The mixture was stirred overnight at room temperature, then poured into ice-water and the organic layer separated and washed with saturated NaHCO 3 solution, water, 10% HCl and again water. The CH ₂ Cl ₂ solution was dried over MgSO ₄ and the solvent was evaporated under reduced pressure to give 5.6 g of a viscous oil. This oil was purified by flash chromatography on silica gel using CH ₂ Cl _{2 to} give 3.7 g (70%) of N- [2-fluoro-4-chloro-5- (n-butylthiomethyl) phenyl] -3,4,5 , 6-tetrahydrophthalimide as a viscous oil.

analysis % C %H % N calculated 59.75 5.54 3.67 found "59.46 5.55 3.38

Production Example 15

N- [2-fluoro-4-chloro-5- (n-butylsulfinylmethyl) phenyl] -3,4,5,6-tetrahydrophthalimide (32)

Into a 100 ml round bottom flask equipped with magnetic stirrer and N ₂ inlet was added 1.4 g (0.0037 mol) of N- [2-fluoro-4-chloro-5- (n-butylthiomethyl) phenyl] -3 , 4,5,6-tetrahydrophthalimide (see Example 14), 0.55 g (0.0037 mol) of sodium perborate tetrahydrate and 25 ml of glacial acetic acid. The mixture was stirred for 2 h at room temperature. Thin layer chromatography showed complete consumption of the starting thio compound. The mixture was poured into ice and extracted into CH ₂ Cl ₂ . The CH ₂ Cl ₂ extracts were washed with water and with brine and dried over MgSO ₄ and the solvent was evaporated to give 1.7 g of oil. This product was purified by flash chromatography on silica gel using ethyl acetate to give 1.1 g (75%) of N- [2-fluoro-4-chloro-5- (n-butylsulfinylmethyl) phenyl] -3,4,5,6- tetrahydrophthalimide as a colorless glassy product.

Analysis · % C %H % N calculated 57.35 5.32 3.52 found 54.26 5.69 3.40

Production Example 16

N - ^ - ^ fluoro-chloro-S-tn-butylsulfonylmethyDphenyU SAS ^ -tetrahydrophthalimidOS)

Into a 100 ml round bottom flask equipped with magnetic stirrer and N ₂ inlet was added 1.4 g (0.0037 mol) of 2N- [2-fluoro-4-chloro-5- (n-butylthiomethyl) phenyl] - 3,4,5,6-tetrahydrophthalimide (see Example 14), 1.7 g (0.0111 mol) of sodium perborate tetrahydrate and 25 ml of glacial acetic acid. The mixture was stirred at room temperature for three days. Thin layer chromatography (1: 1, hexane: ethyl acetate) indicated complete conversion of the starting material to the sulfone. The reaction mixture was poured into ice-water. The resulting white precipitate was filtered off with suction, washed with water and dried in a vacuum oven to give 1.4 g (91%) of N- [2-fluoro-4-chloro-5- (n-butylsulfonylmethyl) phenyl] -3.4, 5,6-tetrahydrophthalimide, m.p. 132-135 ° C.

analysis % C %H % N calculated 55.14 5.11 3.38 found 54.68 4.95 3.11

Production Example 17

N-morpholino-N '- (2-fluoro-4-chloro-5-iso-propoxymethylphenyl) -3,4,5,6-tetrahydrophthalamide (129)

A 50 ml round bottom flask was fitted with magnetic stirrer and N ₂ inlet. In the flask, 1.1 g (0.0031 mol) of N- (2-fluoro-4-chloro-5-isopropoxymethylene) phenyl-3,4,5,6-tetrahydrophthalimide (see Example 2), 20 ml of acetonitrile and 0, 27g (0.0031 mol) of morpholine was added. The mixture was stirred at room temperature overnight. Thin-layer chromatography showed that some starting material was still present so that an additional 0.27 g of morpholine was added and the reaction mixture was stirred at room temperature for an additional 12 hours. The mixture was concentrated in vacuo to a tan oil and the residue recrystallized from 5: 1 hexane: ether to give 940 mg (69%) of N-morpholino-N '(2-fluoro-4-chloro-5-isopropoxymethylenephenyl) -3, 4,5,6-tetrahydrophthalamide as a white solid, mp. 92.0 to 94.5 ⁰ C.

analysis % C %H % N calculated 60,20 6.43 6.38 found 60.65 6.44 6.23

Production Example 18

N- (2-Fluoro-4-chloro-5-isopropoxymethylenephenyl) -3,4,5,6-tetrahydro-2-thionophthalimide (131) Into a 50 ml round bottom flask equipped with magnetic stirrer, reflux condenser with N ₂ inlet and heating mantle, 2.0 g (0.0057 mol) of N- (2-fluoro-4-chloro-5-isopropoxymethylenephenyl) -3,4,5,6-tetrahydrophthalimide, 1.15 (0.0038 mol) was added. Lawessons's reagent (2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,4-disulfide) and 25 ml of toluene were added. The reaction mixture was heated at reflux temperature for ¹ Ah and then stirred for two days at room temperature. The solvent was removed under reduced pressure and the residue was purified by flash chromatography over silica gel using 95: 5 hexane: ethyl acetate to give 0.52 g (25%) of N- (2-fluoro-4-chloro-5-isopropoxymethylenephenyl) -3 , 4,5,6-tetrahydro-2-thionophthalimide as a red oil.

analysis % C %H % N calculated 58.77 5.21 3.81 found 57.23 5.26 3.95

Production Example 19

N- (2-Fluoro-4-chloro-5-isopropoxymethylenephenyl) -3,4,5,6-tetrahydro-2,4-dithionophthalimide (134) Into a 100 ml round bottom flask equipped with magnetic stirrer and reflux condenser with N ₂ - Was added, 2.0 g (0.0057 mol) of N- (2-fluoro-4-chloro-5-isopropoxymethylenephenyl) -3,4,5,6-tetrahydrophthalimide (see Example 2), 5.74g ( 0.0142 mol) of Lawesson's reagent and 50 ml of toluene. This mixture was refluxed for 12 hours. The solvent was removed under reduced pressure and the residue was purified by flash chromatography on silica gel using 95: 5 hexane: ether to give 1.3 g of a yellow solid. This solid was recrystallized from hexane: ether to yield 670 mg (31%) of N- (2-fluoro-4-chloro-5-isopropoxymethylenephenyl) -3,4,5,6-tetrahydro-2,4-dithionophthalimide as a yellow crystalline solid , Mp. 97-101 ⁰ C (Zers.)

analysis % C %H % N calculated 56.31 4.99 3.65 found 56,20 4.95 3.50

Production Example 20.

N- (2-Fluoro-4-chloro-5-isopropoxymethylene) phenyl-3,4,5,6-tetrahydro-2-hydroxyphthalamide (132) A 200 ml round bottom flask was equipped with magnetic stirrer, thermometer, N ₂ inlet and stopper Provided. In the flask, 10.0 g (0.0284 mol) of N- (2-fluoro-4-chloro-5-isopropoxymethylene) phenyl-3,4,5,6-tetrahydrophthalimide (see Example 2) and 40 ml of methanol were added. Sodium borohydride (1.61 g, 0.0426 mol) was added in portions. After the addition of each portion of NaBH ₄ , the temperature rose to about 40 ° C and then dropped immediately to ambient temperature. The reaction mixture foamed vigorously after addition of the NaBH ₄ . The mixture was stirred at room temperature overnight. Thin layer chromatography showed that starting material was still present. An additional 0.54g of NaBH _{4 was} added to the reaction mixture and stirred overnight. Thin layer chromatography again showed the presence of starting material so that an additional 1.1 g of NaBH _{4 was} added and the reaction stirred overnight. The reaction mixture was poured into 125 ml of cold water. A solid resulted, which was filtered off with suction and washed with methanol to give 310 mg of the desired product as a white solid. The aqueous layer was concentrated under reduced pressure and then extracted with ether, dried over MgSO ₄ and the solvent removed leaving 4.5 g of a tan semi-solid product. Thin layer chromatography showed that this solid was approximately 50:50 product and starting material. The solid was taken up in isopropanol and treated with 2.14 g of NaBH ₄ in individual portions. The. The reaction mixture was poured onto ice to form a tan solid which was filtered off and washed with cold methanol to give a white solid. This material was combined with the 310 mg previously recovered and recrystallised from hexane: ethyl acetate to give 440 mg of N - (2-fluoro-4-chloro-5-isopropoxymethylene) phenyl-3,4,5,6-. tetrahydro-2-hydroxyphthalamid, mp. 145.0 to 146.5 ⁰ C.

analysis % C %H % N calculated 61.10 5.98 3.96 found 61.26 5.99 3.91

Production Example 21

2-fluoro-4-chloro-5-isopropoxymethylanilin

A 500 ml round bottom flask was equipped with magnetic stir bar and reflux condenser with N ₂ inlet. To the flask were added 50 ml of carbon tetrachloride, 51.0 g (0.353 mol) of 2-chloro-4-fluorotoluene, 47.6 g (0.353 mol) of sulfuryl chloride and 0.5 g (0.002 mol) of benzoyl peroxide. The resulting mixture was heated to reflux and followed by GC (gel chromatography) until the reaction was approximately 70% complete. At this time (reaction time about 2 hours), the carbon tetrachloride was removed leaving a tan oil. This oil was purified by vacuum distillation to give 44.1 g (70%) of 2-chloro-4-fluorobenzyl chloride as a colorless oil. NMR (CDCl ₃ ): δ 4.60 (s, 2H); 6.77-7.60 (m, 3H). In addition, 11.6 g (23%) of unreacted 2-chloro-4-fluorotoluene was recovered.

Into a 200 ml three-necked round-bottomed flask equipped with magnetic stir bar, thermometer, stopper, and N ₂ inlet dropping funnel was added 26.0 g (0.145 mol) of 2-chloro-4-fluorobenzyl chloride, prepared as above , given. The reaction mixture was cooled to ⁰ ° C. with an ice-salt bath before carefully adding 26 ml of concentrated sulfuric acid. The resulting mixture was stirred for 5 min at room temperature before dropwise adding a nitration mixture of 26 mL of 70% HNO ₃ and 26 mL of concentrated sulfuric acid. The rate of addition was such that the internal temperature of the reaction mixture did not rise above 20 ⁰ C. After the addition was complete, the resulting orange reaction mixture was allowed to warm to room temperature over 30 minutes and was then poured over an ice-water mixture and extracted with CH ₂ Cl ₂ . The CH ₂ Cl ₂ was washed three times with water, dried over MgSO ₄ , and the solvent removed to leave a yellow orange oil. This

Oil was purified by flash chromatography on silica gel using 85:10 hexane: ethyl acetate to give 28.35 g (87%) of 2-chloro-4-fluoro-5-nitrobenzyl chloride as a yellow oil. NMR (CDCl ₃ ): δ 4.70 (s, 2H); 7.44 (d, J = 10Hz, 1H); 8.26 (d,

J = IOHz, 1H).

into a 0.5L HASTALOY biotech the Cabot Corporation) reactor equipped with a pressure gauge, a 2270kg (5000Ib) refracting disk, heating mantle, grounding strap, thermocouple, and glass insert were charged 5.0g (0.022 2-chloro-4-fluoro-5-nitrobenzyl chloride prepared as above and 60 ml (0.784 mol)

Isopropyl alcohol given.

The reaction vessel was sealed and heated to 160 ° C for 48 h and then cooled, vented and the contents transferred to a flask. The resulting dark brown solution was evaporated on a rotary evaporator leaving a dark oil which was purified by flash chromatography on silica gel using 93: 7 hexane: ethyl acetate

has been. This gave 4.57 g (83%) of isopropyl 2-chloro-4-fluoro-5-nitrobenzyl ether as a light yellow oil.

The nitrobenzyl ether prepared above was used to prepare 2-fluoro-4-chloro-5-isopropoxymethylaniline

according to two methods, which are referred to as method A and method B.

Method A

In a pressure bottle, 2.5 g (0.01 mol) of isopropyl ^ -chloro-fluoro-O-nitrobenzyl ether, 25 ml of toluene and 0.25 g of 5% Pt / C were added and in a hydrogenator at 3.0 bar (44 psi) hydrogen pressure hydrogenated. After complete absorption of the hydrogen (about 30 minutes), the hydrogenated mixture was filtered through celite to remove the catalyst to obtain a filtrate containing 2-fluoro-4-chloro-5-isopropoxymethylaniline.

Method B

In a 300 ml stainless steel autoclave equipped with a mechanical stirrer, thermocouple, a 69 bar (1000 psi) refracting disk, a pressure gauge, an inner heating coil (heated by appropriately tempered water), 2.0 g ( 0.0081 mol) of isopropyl-1-fluoro-B-nitrobenzyl ether, 100 ml of toluene and 1.0 g of Raney nickel. The reactor was sealed with N ₂ (3 × 6.9 bar or 100 psi) and purged with H ₂ (3 × 4.1 bar or 60 psi) and then a hydrogen pressure of 6.9 bar (100 psi). generated. The reaction vessel was heated to 100 ^° C. using tempered water and then the hydrogen pressure was increased to 10.3 bar (150 psi). After completion of the H ₂ (about 30 minutes), the hydrogenated mixture was filtered through celite to remove the catalyst to obtain a filtrate containing 2-fluoro-4-chloro-5-isopropoxymethylaniline.

Production Example 22 N- (2-fluoro-4-chloro-5-isopropoxymethylenephenyl) -3,4,5,6-tetrahydrophthalimide (2)

The 2-fluoro-4-chloro-5-isopropoxymethylaniline filtrate obtained according to Example 21 Method A was added to a 100 ml round bottomed flask fitted with a magnetic stir bar and a Dean-Stark trap with reflux condenser and N ₂ inlet was. To the filtrate were added 1.9 g (0.0125 mol) of 3,4,5,6-tetrahydrophthalic anhydride and a catalytic amount of p-toluenesulfonic acid. The mixture was refluxed for 48 hours, then the solvents were removed to give a dark amber oil. This oil was purified by flash chromatography on silica gel using 95: 5 toluene: ethyl acetate to give a clear oil which solidified under vacuum. A total of 2.65 g (75%) of N- (2-fluoro-4-chloro-5-isopropoxymethylenephenyl) -3,4,5,6-tetrahydrophthalimide was obtained as a white solid.

analysis % C %H % N calculated 61.45 5.44 3.98 found 61.81 5.44 3.53

Production Example 23

N- (2-fluoro-4-chloro-5-isopropoxymethylenphenyl) -3,4,5,6-tetrahydrophthalimide (2)

The 2-fluoro-4-chloro-5-isopropoxymethylaniline-containing filtrate obtained according to Example 21, Method B was concentrated to about 25 ml in a rotary evaporator and then placed in a 50 ml round bottom flask equipped with magnetic stirring bar and Dean-strength Trap with reflux condenser and N ₂ inlet. To the filtrate was added 1.23 g (0.0081 mol) of 3,4,5,6-tetrahydrophthalic anhydride and a catalytic amount of p-toluenesulfonic acid. The mixture was refluxed for 24 hours and then the solvents were removed by rotary evaporation to give a brown oil. Purified by flash chromatography on silica gel using 75:25 hexane: ethyl acetate to afford 1.81 g (64%) of N- (2-fluoro-4-chloro-5-isopropoxymethylenephenyl) -3,4,5,6- tetrahydrophthalimide as a pale yellow solid.

Preparation 24 N- [2-fluoro-4-chloro-5- (N-butylaminocarbonyloxymethyl) phenyl] -3,4,5,6-tetrahydrophthalimide (78)

Into a 150 ml pressure cylinder equipped with magnetic stirring bar, a valve rising at 6.9 bar (100 psi) and a pressure gauge, 1.0 g (0.0045 mol) of 2-chloro-4-fluoro-5-nitrobenzyl chloride, 2.5 ml Dioxane and 2.5ml of water. The cylinder was sealed and heated to 160 ⁰ C for 72 h, then cooled, vented and the contents poured into methylene chloride. The CH ₂ Cl ₂ layer was separated, dried over MgSO ₄ and the solvent removed leaving a yellow oil. This oil was purified by flash chromatography over silica gel using 75:25 hexane: ethyl acetate to give a yellow solid which was rinsed with hexane and filtered. There was obtained 0.74 g (81%) of 2-chloro-4-fluoro-5-nitrobenzyl alcohol. NMR (CDCl ₃ ): δ 2.29 (t, J = 6Hz, 1H), 4.83 (d, J = 6Hz, 2H); 7.35 (d, J = 10Hz, 1H), 8.30 (d, J = 8Hz, 1H). Into a 250 ml pressure bottle fitted with a magnetic stir bar was added 10.0 g (0.0486 mol) of 2-chloro-4-fluoro-5-nitrobenzyl alcohol, 100 ml of CH ₂ Cl ₂ , 5.3 g (0.0535 mol). Added n-butyl isocyanate and 5.4 g (0.0535 mol) of triethylamine. Upon addition of the triethylamine, the reaction mixture changed color from organ to deep brownish-red. The reaction bottle was stoppered and then stirred for 16 h at room temperature. The volatiles were removed on a rotary evaporator leaving a dark oil. This oil was purified by flash chromatography over silica gel using 75:25 hexane: ethyl acetate to give a yellow oil which solidified on standing. The solid was rinsed with hexane and filtered to give 9.78 g (66%) of 2-chloro-4-fluoro-5-nitrobenzyl-N-butylcarbamate.

NMR (CDCl ₃ ): δ 0.70-1.67 (m, 7H); 3.06-3.43 (m, 2H); 4.76-5.34 (br, 1H); 5.20 (s, 2H), 7.36 (d, J = 10Hz, 1H), 8.15 (d, J = 8Hz, 1H). -

In a pressure bottle, 6.98 g (0.023 mol) of 2-chloro-4-fluoro-5-nitrobenzyl-N-butylcarbamate, 100 ml of toluene and 0.5 g of 5% Pt / C were added and in a hydrogenation apparatus at a hydrogen pressure of 3 Hydrogenated at 0 bar (44 psi). After complete uptake of the hydrogen (requiring a new pressure increase to 2.8 bar [40 psi], total time about 1 h), the hydrogenated mixture was filtered through CeMt to remove the catalyst and remove the filtrate containing 2-chloro-4-. Fluoro-5-aminobenzyl-N-butylcarbamate was added to a 250 ml round bottomed flask equipped with magnetic stirrer bar and a Dean-strength trap with reflux condenser and N ₂ inlet. To the filtrate was added 3.49 g (0.023 mol) of 3,4,5,6-tetrahydrophthalic anhydride and a catalytic amount of p-toluenesulfonic acid. The mixture was refluxed for 48 hours and then the solvents were removed on a rotary evaporator to leave a dark gold oil. This oil was purified by flash chromatography over silica gel using 90:10 toluene-ethyl acetate to give a yellow oil which slowly solidified on standing. The solid was rinsed with hexane and filtered to yield 5.96 g (64%) of N- [2-fluoro-4-chloro-5- (N-butylaminocarbonyloxymethyl-phenyl-SAB-tetrahydrophthalimide.

analysis % C %H % N calculated 58.75 5.42 6.85 found 59.23 5.47 6.80

Production Example 25 N- (2-fluoro-4-chloro-5-morpholinomethylenephenyl) -3,4,5,6-tetrahydrophthalimide (67)

Into a 100 ml three-neck round bottom flask fitted with thermometer, magnetic stir bar and N ₂ inlet dropping funnel was added 10.4 g (0.0453 mol) of 2-chloro-4-fluorobenzylmorpholine. The flask was ice-cold -Salzwasser-bath cooled to 0 ⁰ C before carefully 10 ml of concentrated sulfuric acid were added, whereby a very viscous mixture arose which was difficult to stir. The reaction mixture was allowed to warm to about 10 ⁰ C, before a nitration mixture of 10 ml of 70% HNO ₃ and 10 ml of concentrated sulfuric acid was added dropwise. During the addition, the reaction mixture had to be stirred by hand because of the high viscosity. At the end of the addition, the reaction mixture was more fluid and could be effectively stirred with the stir bar. After complete addition, the ice bath was removed and the reaction mixture was stirred for 4 h at room temperature, then poured into ice-water and treated with a 15% sodium hydroxide solution until the aqueous layer became alkaline, the resulting 2-chloro-4-fluoro-5- nitrobenzylmorpholinsulfat was released. The mixture was extracted with CH ₂ Cl _2, dried over MgSO ₄ and the solvent removed. Mari received 11.6 g (93%) of 2-chloro-4-fluoro-5-nitrobenzylmorpholine as a pale yellow solid. NMR (CDCl ₃ ): δ 2.37-2.76 (m, 2H), 3.53-3.87 (m, 2H), 7.35 (d, J = 10Hz, 1H), 8.26 ( d, J = 8Hz, 1H).

This material was found to be 98.7% pure by gas chromatography. Further purification was achieved by flash chromatography on silica gel using 75:25 hexane: ethyl acetate to give 10,56g (85%) of the Morpholinproduktes as a light yellow solid, mp 91-93 ⁰ C..

analysis % C %H % N calculated 48,10 , 4.41 10.2 found 48.14 4.45 10.05

In a pressure bottle, 2.0 g (0.0073 mol) of 2-chloro-4-fluoro-5-nitrobenzylmorpholine, 30 ml of toluene and 0.2 g of 5% Pt / C were added and hydrogenated at a hydrogen pressure of 3.0 bar (44 psi). hydrogenated. After complete hydrogen uptake (approximately 30 minutes), the hydrogenated mixture was filtered through celite to remove the catalyst and the product containing 2-chloro-4-fluoro-5-aminobenzylmorpholine was added to a 100 ml round bottom flask equipped with magnetic stirring bar and a Dean. Strong trap with reflux condenser and N ₂ inlet was provided. To the filtrate was added 1.11 g (0.0073 mol) of 3,4,5,6-tetrahydrophthalic anhydride and a catalytic amount of p-toluenesulfonic acid. The mixture was refluxed for 48 hours and then the solvents were removed to give a light brown oil. This oil was purified by flash chromatography on silica gel using 70:30 hexane: ethyl acetate to give 0.56 g (20%) of N- (2-fluoro-4-chloro-5-moprpholinomethylene-phenyl) -3,4,5, 6-tetrahydrophthalimide as a white solid, mp. 108-111 ⁰ C.

analysis % C %H % N calculated 60.24 5.32 7.40 found 60.83 5.41 7.13

Production Example 26

N- (2-fluoro-4-chloro-5-cyanomethyl) phenyl-3,4,5,6-tetrahydrophthalimide (96)

Into a 1000 ml round bottomed flask equipped with an air stirrer, reflux condenser with N ₂ inlet and dropping funnel was added a solution of 99.9 g (0.0691 mol) of 2-chloro-4-fluorotoluene in 400 ml of carbon tetrachloride previously passed through a 48 cm (6 inch) neutral clay column, 135.3 g (0.760 mol) of N-bromosuccinimide and 0.50 g of dibenzoyl peroxide. The mixture was refluxed overnight. The succinimide was filtered off and the solvent removed to yield 155g of a light orange solid. NMR (CDCl ₃ ): δ 4.52 (s, 2H), 6.68-7.60 (m, 3H). This raw product, which accounts for about 12% of

Contained starting material was used without purification in the next stage.

A 1 000 ml round bottom flask was fitted with magnetic stirrer bar and reflux condenser with N ₂ inlet. To the flask was added the crude benzyl bromide prepared above in 250 ml toluene, 8.0 g Aliquat 336 in 50 ml toluene, and 32.0 (0.653 mmol) sodium cyanide. The mixture was stirred at room temperature overnight, then washed three times with water and dried over MgSO ₄ and the solvent removed to give an orange oil. This oil was taken up in hexane: ethyl acetate and crystallized to give the desired benzyl cyanide as a white solid, 71.4g (61% by weight)

the starting toluene). NMR (CDCl ₃ ): δ 3.80 (S, 2H), 6.80-7.73 (m, 3H).

Into a 250 ml round bottom flask equipped with magnetic stirring bar, reflux condenser with N ₂ inlet, thermometer and a funnel for adding solids, 40 ml of fuming nitric acid was added and cooled to 15 ° C. The benzyl cyanide

was added as a solid in individual portions while the temperature remained at 15 ° C. After complete benzyl cyanide addition, the reaction mixture was heated to 33 ° C for 3.5 h and then poured onto ice. The desired nitro compound formed as a solid. This solid was thoroughly washed with water, taken up in 250 ml CH ₂ CI _2, dried over MgSO ₄ and the solvent removed to give a pale yellow solid. This solid was triturated with hexane and filtered to yield 9.5 g (75%) of the desired 2-chloro-4-fluoro-5-nitrobenzyl cyanide, m.p. 62 ^° C. as a pale yellow solid. NMR (CDCl ₃ ): δ 3.95 (s, 2H), 7.52 (d, 1H), 8.33 (d, 1H).

Into a 250 ml round bottomed flask equipped with magnetic stir bar and N ₂ inlet reflux condenser was added 3.2 g (0.0149 mol) of 2-chloro-4-fluoro-5-nitrobenzyl cyanide, 16.8 g (0.075 mmol) of stannous II chloride dihydrate and 60ml ethanol. This mixture was heated at 70 ° C for 5 hours and then stirred at room temperature overnight. About ² hours of the ethanol was removed under reduced pressure and the residue was poured into ice-water. The residue was basified with 1N NaOH and extracted into ethyl acetate. The ethyl acetate was washed twice with water, dried over MgSO ₄ and the solvent removed. There remained 2.5 g (91%) of the desired 2-chloro-4-fluoro-5-aminobenzyl cyanide as a yellow solid. NMR (CDCl ₃ ): δ 3.50 - ^, 05 (s broad, 2H), 6.85 (d, 1H), 7.06 (d, 1H).

Into a 100 ml round bottomed flask equipped with magnetic stirrer bar, Dean-Stark trap and N ₂ inlet reflux condenser was added 2.5 g (0.0135 mol) of the 2-chloro-4-fluoro-5-aminobenzyl cyanide prepared as above, Added 2.06 g (0.0135 mol) of 3,4,5,6-tetrahydrophthalic anhydride, 40 ml of toluene and a catalytic amount of p-toluenesulfonic acid. The mixture was refluxed overnight, washed with water, 5% HCl, water, saturated NaHCO _3, and again with water, dried over MgSO ₄ and the solvent removed to give an amber oil. This oil was purified by column chromatography (3: 1, hexane: ethyl acetate) to give a pale yellow solid. Mp 144-147 ° C, 2.20g (51%).

Analysis% C% H% N

calculated 60.29 3.80 8.79

found 60.33 4.09 8.84

Production Example 27

Methyl-a-methyl- [2-chloro-4-fluoro-5- (3,4,5,6-tetrahydrophthalmidoyl)] phenylacetate (117)

A 2L round bottom flask was equipped with stir bar, reflux condenser with N ₂ inlet, thermometer and dropping funnel. In the flask, 200 ml of dry tetrahydrofuran containing 32,8g (0,324mol) of dry diisopropylamine, cooled to 0 ⁰ C, and added 203ml (20.8 g, 0,324mol) 1.6M n-butyllithium in hexane dropwise. After this addition was complete, the reaction mixture was stirred for 10 min at ⁰ ° C and then cooled with a dry ice-acetone bath to -76 ⁰ C. A solution of 50.0 g (0.295 mol) of 2-chloro-4-fluorobenzyl cyanide in 125 ml of dry tetrahydrofuran was added dropwise. The reaction mixture turned dark green and then orange. The mixture was stirred for 1 h and then 125.6 g (0.885 mol) of methyl iodide were added dropwise. The reaction mixture turned yellow and was stirred for 30 minutes at -78 ° C and then concentrated under reduced pressure. About 350 ml of ice-water were added to the residue, which was then extracted twice with 250 ml portions of dichloromethane. The organic extract was washed with water, dried over MgSO ₄ and the solvent removed to leave a-methyl-2-chloro-4-fluorobenzyl cyanide as a dark orange liquid which was used in the next step without purification. NMR (CDCl ₃ ): δ 1.60 (d, 3H), 4.31 (q, 1H), 6.82-7.88 (m, 3H).

Into a 250 ml round bottom flask equipped with thermometer, reflux condenser and magnetic stirrer was placed 75 ml of fuming nitric acid and cooled to 5 ° C. For this purpose, 23.0 g (0.125 mol) of α-methyl-2-chloro-4-fluorobenzylcyanid were added dropwise within 30 min, the temperature below + 10 ⁰ C remained. After complete addition, the mixture 4 was frequently heated to 33 ⁰ C. The mixture was cooled to room temperature, poured onto ice and extracted with dichloromethane. The combined organic phase was washed thoroughly with water, dried over MgSO ₄ and the solvent removed leaving 23.3 g of a dark brown oil. This product was purified by flash chromatography on silica gel using 80:20 hexane: ethyl acetate to give 19.6 g (68%) of a-methyl-2-chloro-4-fluoro-5-nitrobenzyl cyanide as a yellow oil. NMR (CDCl ₃ ): δ 1.6 (d, 3H), 4.3 (q, 1H), 7.3 (d, 1H), 8.2 (d, 1H).

Into a 500 ml round bottom flask equipped with magnetic stirrer and reflux condenser with N ₂ inlet was added 15.0 g (0.0656 mol) of a-methyl-2-chloro-4-fluoro-5-nitrobenzyl cyanide and a solution of 100 ml concentrated sulfuric acid in 145ml of water. The mixture was refluxed for 12 hours, then cooled to room temperature and poured into ice-water. The resulting solid was filtered off with suction, washed well with water, taken up in ethyl acetate, dried over MgSO ₄ and the solvent removed to leave a tan solid. This solid was triturated with hexane and filtered to give 15.6 g (96%) of a-methyl-1-chloromethyl-δ-nitrophenylacetic acid as a white solid. NMR (CDCl ₃ ): δ 1.0 (d, 3H), 3.5-4.0 (Q, 1H), 6.11 (s wide, 1H), 7.0-8.0 (pair d, 2H).

In a pressure bottle 14.3 g (0.0578 mol) of a-methyl ^ -chloro-fluoro-o-nitrophenylacetic acid, 250 ml of ethyl acetate and 1.4 g of 5% Pt / C were added. The bottle was placed in a hydrogenator and hydrogenated (the contents) at a hydrogen pressure of 2.8 bar (40 psi) for 1.5 hours. The mixture was filtered through celite and the solvent removed to give 11.4 g (91%) of a-methyl-2-chloro-fluoro-o-aminophenylacetic acid as a white solid.

Into a 500 ml round bottom flask equipped with magnetic stirrer and reflux condenser with N ₂ inlet was added 11.4 g (0.0526 mol) of α-methyl-chloro-fluoro-o-aminophenylacetic acid, 8.8 g (0.0578 mol) 3, Added 4,5,6-tetrahydrophthalic anhydride, 200 mg of p-toluenesulfonic acid and 300 ml of toluene. The reaction mixture was refluxed with removal of the resulting water for 12 hours. After cooling to room temperature, the mixture was washed with water, dried over MgSO ₄ and the toluene removed leaving 17.1 g of an orange oil, this oil was triturated with hexane to leave a pale orange solid (16.0 g, 86%). ) which was used in the next step without further purification.

The a-methyl [2-chloro-4-fluoro-5- (3,4,5,6-tetrahydrophthalimidoyl)] phenylacetic acid (16.0 g, 0.0456 mol) prepared as above was dissolved in 200 ml carbon tetrachloride and added to a 500 ml round bottom flask equipped with magnetic stirrer, reflux condenser with N ₂ inlet and dropping funnel. A solution of 21.6 g (0.182 mol) of thionyl chloride in 50 ml of CCI ₄ was added dropwise. The mixture was then refluxed for 2 hours. The IR spectrum of the mixture showed complete conversion of the acid chloride. The solvent and excess thionyl chloride were removed under reduced pressure

 A solution of 4.5 g (0.0122 mol) of the acid chloride prepared above in 20 mL of methylene chloride was added to a 100 mL

Round bottomed and stirred under N ₂ . This solution was cooled to ⁰ ° C. and a solution of 1.9 g (0.0678 mol) of dry methanol and 1.86 ml (0.0134 mol) of triethylamine in 10 mM methylene chloride was added dropwise. The mixture was stirred at room temperature for 12 h, washed with water, dried over MgSO ₄ and the solvent removed to give 2.85 g of an oil. This oil was purified by flash chromatography over silica gel to give 1.4 g (32%) of the desired methyl-a-methyl- [2-chloro-4-fluoro-5- (3,4,5,6-tetrahydrophthalimidoyl)] - phenyl acetate as a viscous oil. NMR (CDCl ₃ ): δ 1.5-2.3 (2m and 2s, 11H), 3.6 (s, 3H), 4.2 (q, 1H), 7.3 (doublet pair, 2H).

Analysis% C% H% N

calculated 59.11 4.69 3.83

found 58.87 5.05 3.80

Herbicidal activity

The biological efficacy and selectivity of representative compounds as (terrestrial) herbicides have been evaluated as preemergence herbicides and as teaspoon herbicides. The post-emergence test plants were morning glory, mustard, recurved foxtail, nightshade, spotted lobster, spawn (Indian mallow) and tea weed. The pilot plant for pre-emergence trials was the same except that mustard and nightshade were replaced by coffee weed, foxtail, broadleaf signalgrass, and large cinquefoil. For the pre-emergence experiments, seeds of the plants listed in Table II were sown in fresh soil about 1 inch below the surface. In the pre-emergence experiments, the soil was sprayed with a solution of the test compound immediately after seeding the seeds. The solution contained about 1% by weight of the test compound in a 1: 1 water acetone solvent. The compounds were applied in the amounts indicated in Table II.

About 3 weeks after spraying, the herbicidal activity of the compounds was determined by visual observation of the treated areas as compared to untreated areas. These observations are given according to an O to 100% scale for the control of plant growth.

In both postemergence experiments, the soil and the developing plants were sprayed about 2 weeks after sowing the seeds. The compounds were applied in the amount indicated in Table I for each test compound from a solution containing about 1% by weight of the compound to be tested in acetone. The post-emergence herbicidal action was measured in the same manner as the pre-emergence effect, 3 weeks after the treatment. The results of both pre-emergence and postemergence tests are given in Tables I and II, with a dash (-) indicating that the compound was not tested against this particular plant. In each of Tables I and II, the formula gives a number which corresponds to the formula in Table III, which gives the physical properties and elemental analyzes for compounds. For the test plants, the following abbreviations are given: Soybeans (SB), Corn (CN), Wheat (WH), and Rice (Rl). The abbreviations for the weeds are: Morning Glory (MG), Mustard (MU), Foxtail Curved Back (PW), Nightshade (NS), Greater Burdock (COC), Spawn (VE), Tea Weed (TW), Coffee Weed (CW ), Foxtail (FT), broadleaf signalgrass (BS) and large cinquefoil (LC).

Application example 1

Table I shows the data of herbicidal activity for various preferred compounds which give excellent control of broadleaf weeds and good selectivity to crops at low application rates in postemergence treatment.

- / 4- £ .ΌΙ Ο / Ο

table

Post-emergence / selectivity to crops of the new C-methylanilines

formula

Application amount of crops weeds

kg / ha (IVA)

SS cw wt) Ri rc wu pw ms coc%% Damage% Control

CbC

(0.015) 0.017

10 10 10 U 100 100 91 100 11 100 -

CH ₂ OCCH ₁

(0.015) 22 10 14 U 100 52 100 100 100 100 0.017

'

cot

Cl - (0,06)

0.07 CH ₁ SCH ₂ CH,

10 14 32 11 100 100 100 100 - 100 100

-75- ΔΧ31 ü / ό

Table I (continued)

Fomnel

Application amount of crops weeds

kg / ha SB CT mh bi nc wü pw ns coc ve Tw

(lb / A)% Damage% Tack

(0.06) 22 10 14 U

0.07 CH ₂ SCH ₂ COyCHj-

100 100 100 100 - 100 100

It

(0.015) 0 0 0

¹ _ο 0.017

»Ιΐ

100 10 100 100 100 100 -

39

oat

(Ο, ΟΙδ) 26 14 100 O 100 100 100 100 Sb 0.017

(0.06) 21 10 10 10 26 U 100 100 4S

0.07

CH ₁ Br

ODC

(θ.015) 11 10 14 11 82 98 100 100 100 0.017

- / Ο - £ 9 / a / O

Table I (port setting)

Fonrel applicator crops weeds

kg / ha sb cn wh ri mg hu pw ns coc ve tw

(lb / A)% Damage% Combination

Il

(0.015) 21 33 22 20 100 45 100 100 32

I 0.017

CH ₂ OCHiCH = CH ₂

'0.015 ' 38 22 6 0 100 100 100 100 100

ο, Όπ

O CHjOCH ₁ CH ₁

, 11

QQ Ο <

(0.25) 11 10 26 21 100 50 100 100 95 0.28

CHjOH

^ "" "V,., (0,015

° ' ⁰¹⁷ O CH ₂ OCCHjCH,

14

E> £

19 10 11 10 19 11 100 100 - 50

Cl

Fri.

(0.25) 20 10 14 10 76 22 100 100

0.28

1OO -

CH ₂ OH

L5

£ Xil Ο / ύ

Table T (continued)

formula

Applying crops

SB cn WH Ri rc

kg / ha (lb / A) weeds

PW NS C OC VE _TW

% Damage% Combat

Cl

11

(0.06) 0.07

11 0 11 0 11 11 100 100 - 100 -

16

CH ₁ OCH (CH ₅ ),

u o

0.015 ^; 19 20 21 0 32 10 100 100 - 100 0.017

17

CH ₂ OCH (CH ₂ ),

9 f

ti o

I (0,015)

0.017 CH ₁ OCH ₁ CH (CHj) ₂

11 11 10 10 11 10 100 100 - 100 -

18

Il

CH ₁ OCH,

(0,015) 0,017 22 10 11 0 100 100 100 100 -

19

Il

(0.015) 11 0 21 0 10 0 100 100 0 100 0.017

CH ₁ F

21

formula

T a b e 1 le

T (continued)

Bring crops to weeds

kg / ha SB CN WH RI HG HU PW NS COC VE TW

% Damage

% Tamping

(0.015) 0.017 11 11 10 35 10 11 100 U 100

CH ₂ OCH (CH ₂ ),

0.28

23

(0.25) 0.28

CH ₁ OH

24

CH ₁ OCWU ₁

(0 _f 015) 0.017

25

2 11 21 10 35 20 100 100 10 100 11 11 11 10 95 11 U 100 10 100 19 10 26 10 100 100 100 100 100 100

(0.015) 0.017

CH ₂ NHCH ₁ CeCH

26

11 20 21 10 delete 14 76 100 10 100

table

X (continued)

formula

Aufbrincpnenge kg / ha

Useful plants SB CN WH t

% Damage

nc

Weeds nu pw ns

coc νε tu

% Bekärcpfung

CH, O

27

(0.015) 0.017 11 0 0 0 10 14 100 100

100

(0.015) 0.017

CH ₁ OCH ₁ CsCH

28 10 0 11 14 100 10 100 95

100

CH ₂ OCH (CH ₁ ),

1.1

29 10 10 22 10 22 10 100 100 14 100

(0.06) 10 10 20 10 31 14 100 100 26 100

0.07

30

CH ₂ OCH ₃ H ₃ ),

(0.01b) 0.017

CH ₂ S (CH ₁ ) H,

31 ίο ίο π ίο H 44 loo 100 26 100

-80- ZiJ / 5/3

Table I (continued)

formula

Application amount of crops weeds

SB CN WH RI NC MU PW NS COC Vf "Tw

kg / ha

% Damage

% Catches

Il

(0.015) 11 10 0 0 100 100 100 100 32 100 0.017

32

ti o

¹ (0,01b)

0,017

10 10 0 0 C 10 100 100 22 100

CH ₁ SO ₁ (CH ₂ CH _{2 )}

33

, _Λ (0.015)

38 10 20 20 95 50 100 100 32 100

CH ₁ C-NHCH,

0,017

34

35

(0.015) 10 0 10 10 14 32 100 100 10 100 0.017

(0.015) 10 10 20 10 82 38 100 100 53 100 0.017

CH ₁ OCCH (CH 2),

36

formula

Table I (continued)

Application amount of crops ¹ weeds

kg / ha SB CN wh ei nc hu Pw NS coc ve tu

(lb / A)% damage. % Bekäip

Co-C

ι (0,015)

0.017 11 10 20 10 22 SO 100 100 22 100

CH ₁ OUc (CH 2);

37

-NH-

CH ₁ OP

OCH ₁ CH,

(0.06) 10 10 10 10 10 44 100 100 100 100

(CH,),

129

(0.015) 0.017 10 10 20 0 45 26 100 26 44 100

CH _x OCH (CH,),

(0.015) 0.017 21 20 11 11 100 98 100 100 100 100

// Vo. (0.015)

0,017

CH ₁ OCH (CH ₂ ),

40

40 20 11 20 22 10 100 26 22 100

Table X (continued)

formula

Äufbringnenge crops weeds

kg / ha SB CT wh i hg fiu pw NS coc £ Tw

(lb / A)% Damage% Combination

S F

(0.015) 0.017 CH ₁ OCH (CH ₁ ),

10 10 21 10 100 26 100 94 10 100

131

cab

: t

O CH

41

 ° <J

(0.015) 10 10 0.017

10 45 20 100 100 45 100

(0.015) 0.017

21 10 U 10 100 0 100 100 100 100

42

Ch ₁ OCH ₁ COCH ₁ CH,

0.015) 21 20 10 10 100 33 100 100 40 100 0.017

O CH ₁ SCH (CH ₁ ),

44

ν 10 0 10 10 99 10 100 100 19 100

-83-ΔΌΙ Ο / ύ j

Table I (port setting)

formula

Application crops weeds

kg / ha (lb / A)

SB CW WH RI WG ITU PW MS COC VE TVJ

% Damage% Combat

(0.015) 20 10 20 31 100 22 100 100 100 100 U / U * /

46

for W

(0.015) 14 10 20 10 71 10 100 100 100 100 0.017

47

CH ₁ OCH,

O CH ₁ OCH ₁ CF,

(0.015) 20 (/, 017

10 10 32 20 100 100 100 100

, (0.015) 26 10 35 21 78 19 100 100 55 100

0.017 CH ₁ OCH ₁ CH ₁ Cl

QOC

O CH ₂ S

(0.015) 21 10 10 0 33 85 100 22 21 100 0.017

Table I (continued)

formula

Application amount of crops weeds

, λ- SB C \ HH RI WG WU PW NS COC VE Tw

kg / ha;

(lb / A)% damage% Tamping

52

CHF,

(0.015) 32 10 22 10 14 H 100 100 22 100 0.017

53

(0.015) 20 10 21 10 33 22 100 100 33 100, 0.017

1 (0.01S)

0.017 CH ₁ OCH ₁ CO ₁ Ch ₁ CH =

10 10 11 10 68 11 100 100 100 93

54

(0.015) 20 10 10 10 100 10 100 100 32 0.017

CH ₂ OCH ₁ CO ₁ CH ₁ C SEC

55

table

I (port setting)

formula

Application amount of crops weeds

kg / ha S8 CTi wh Bl nc nu Pw FTI CQC ve tw

(lb / A)% damage% control

(0.015) 20 10 20 21 98 10 100 82 100 100 0.017

H ₁ OCH ₁ CO ₁ CH (CH,),

(0.06) 0.07

CH ₁ OCH (CH ₁ ),

132

10 10 21 10 2 11 100 64 14 100

12 0 22 22 11 33 100 100 19 100 31 20 10 10 «0 22 100 100 19 100 ·

(0,015)

0.017 CH ₁ NCHjCOiCH ₂ CH,

59

10 11 20 85 35 100 100 100 100

T abe 1 1 e I (continued)

formula

Application rate of crops kg / ha

weeds

SB CN WH RI (Ib / A)% damage

HG MU PW NS COC VE TW% Control

OX

(0.015) 40 10 0.017

100 22 100 100 100 100

CH ₁

Ch ₁ OCH-COCH ₁ CH, 60

61

(0.015) 25 10 10 10 100 21 100 100 Cl 0.017

CH,

CH ₁ OC-COCH ₄ CH, CH ₁

99

.ο Λ

62

(0 _r 015) 21 10 10 10 19 22 100 100 33 88

0,017

CH.

(0.015) 31 0 10 10 40 14 100 100 14 82 0.017

63

Table I (continuation )

formula

Application amount of crops

weeds

SB CN WH RI HG (lb / A)% damage

PW

Vetu

0.015) 0/0 22 26 100 100 22 32

CH ₄ OCH ₁

65

.ο Κ

Cl

CH, C1

66

(0.015) CH, O, Ol 7 10 20 14 32 0 100 100 97

(0.015) 26 10 10 0.017 40 100 100 40 100

CH

67

T a b e 1 1 e I (continued)

formula

Supply of useful plants

weeds

kg / ha SB CN WH RI MG MU PW NS COC VE TW (IbM) % Damage% Combination

CD'

O CH _a OCH CC

69 (0.015) 22 10 21 10 100 55 100 0.017

0-015) 26 10 10 26 14 10 95 0, ^f 017

(0.015) 43 0.017

70 23 22 95 54 100

100

100

100

(0.015) 45 20 11 14 38 100 100 0.017

CH _a ONO, · 100

71

table

I (continued)

formula

Aufhringmenge crops

weeds

C-NH (CHJ ₁ CH ₁ F

V-Cl

CH ₁ OCH (CH ₁ ),

si cm w rT hg mu pw ns coc ve tw

(Ib / A)% injury% profiling

(0.015) 10 0 0 10 10 66 100 100 10 33 0.017

D5

.P F

72

(0.015) 10 0 0 0 11 11 100 100 14 100 0.017

OO

Cl 0

CH ₁ OCNH 73

(0.015) 19 0.017

40 82

100 40

(0 _f 015) 10 0.017

0 0 33 2 0 100 10 98

Table I (continued)

formula

Bringing up crops in ¹ weeds

kg / ha SB CN WH RI MG HU PW NS COC VE TW (lb / A)% damage% cough

(0.015> 0.017 0 0 38 14 88 100 0 62

CH ₁ OCH ₁ CHCH. OH OH

75

(0.25) 10 0 0 ^f , 28 0 95 100 100 100 53 100

(0.015) 10 10 0.017

0 26 11 100 100 - 22

Cl

CH ₁ OCH (CH ₁ ),

136

(0.06) 10 10 10 0.07 55 45 100 100 - 100

CH ₁ NHCH (CHJ ₁ 77

formula

CÖ

kg / ha (lb / A) b e I lie (Continuation) 91 - 257 573 T a (0 _f 015) 0.017 i) | CH. crops weeds application rate SB CN WH RI% damage HG MU PW NS COC% combat VE TW 6 10 14 0 99 85 100 100 - 100 - N CH ₁ OCNH (CH

78

(0.015) 1O 0 ', 017

0 10 0 10 100 100

CH ₁ OCO (CH ₁ CH,

79

(XYC

Cl

80

(0.05) 20 10 0 10 78 22 100 100 - 100 0.07

(0.015) 21 20 0.017

100 100 100 100

CH ₁ OI II

CHjO-N = C-COCH ₁ CH ₁

81

-az- ^ .a / a / o

Table I (port setting)

Formula Aufbrijngmenge crops weeds

kg / ha CN CN WH RI MG MU PW NS COC VE TW (lb / A)% Damage % Control

CD

W 0

Q), 25> 20 10 O ', 28

10 12

14 100

Voch .- // Vci

CH ₁ OCH (CH ₁ ), 82

fc.06) 10 10 10 22 11 12 100 100 55 22 0.07

CH ₁ OCH (CH,), D7

(0.015) 20 0.017

0 0 21 0 10 96 100 26 12

CH ₁ OCH (CHj) ₁₁ D8

(0.015) 23 10 10 11 0.017

11 26 100 45 100

-ad- £ .ΌΙ Ό / ύ

table

I (port setting)

Application amount of crops weeds

formula

QO-C

CH ₁ OH 84

kg / ha S8 CN WH RI MG MU PW NS COC VE TW (lb / A)% Damage% Control

(0.06) 21 10 10 20 19 10 32 100 20 55 0.07

CH,

(0.015) 20 0.017

CHJNHCHCHJOCH, 85 0 11 10 100 10 14 51 100 25

(0.015) 22 _8r 0.017

COQ-

CH ₁ OCH ₁ CO- ^ J

0 0 10 98 20 21 100 100 99

(0.015) 0i017

CH _a OCH (CH 2), D 9 0 10 0 26 33 53 100 100 100

formula

och;

application rate kg / ha (lb / A) a belle - I (continued) 94- 257 573 (0.015) 0.017 crops weeds , CH, SS CN WH Ri% damage MG HU PW NS COC% Control , T 0 CH ₁ OCSCH ₁ 2 10 0 20 40 26 100 100 12 VE TW 87 100 -

(0.015) 0 0 Oi

¹ CH ₁ OC-NH (CH ₁ ), CH ₁ 88

35 45 100 100 0 100

0 H

NH

C-NH

Il

Cl

140

(0 _f 25) 10 0 0 14 10 45 14 100 100 100 0,28

<0.06) 14 10 OV

CH ₁ OCH ₁ CNH- (Q 89

95 45

100 99

-95- ZÜ / Ö / 'Ο

Table I (continued)

formula

Application amount of crops

kg / ha S8 CN WH RJ (lb / A)%

weeds

MG HU PW NS COC VE TW% Control

(0.015) 21 0.017 10 2 10 45 14 54 100 14 88

0 ι

CH ₁ NHCH ₁ COCH ₄ Ch, 90

or:

H O

Q), 015) d, 017 10 14 0 99 78 100 100 100 100

CH ₂ OCH (CH,), 141

N (CH ₄ CH,),

W 0

Cl

fc, 25 0/28 10 10 0 11 10 99 100 100 11

CH ₁ OCH (CH ₂ ), 142

(0 _f 06) 0.07 0 26 0 45 20 100 100 100 35

CH ₁ OCH (CH ₁ ), 143

-96- Zb / iJ / 3

table

I (sharing)

formula

Crop amount of weed weeds

kg / ha SB CN HH RI MG HU PW HS COC VE TW (IbM) % Damage% Control

(O.OI5) 2 11 10 0, bi7 2 10 100 100 38 55

(0 _f 06) 2 0.07 10 0 100 45 100 100 100 100

CH ₁ OCNH-ZTN 92

(0.06) 0 0 0 6 12 100 100 2 100

(0.015) 0.017

0

CH ₁ OCCH ₁ COCHjCH, 94

0 0 0 26 10 99 100 0 100

Table I (continuation )

formula

Crop amount of crops ² weeds

kg / ha S8 -0! 'HjT Rl (ft / A). * Damage

R] MG MU PW NS COC VE TW. % Fight

(0015) 0 0.017 0

14 10 2 20 95 100 100 44

(0.0.15) 0 10 W 0 40 20 100 100 100 100 0.017

11 96 45

100

0.06) 0.07

0 0 0 78 32 40 100 30 100

CH ₄ COCH ₁ C = CH 98

table

(Continuation)

formula

Aufbrirxpenge crops ² weeds

kg / ha CN CN WH Rl (1 b / A)% injury MG MU PW NS COC VE TW % Control

(0.06) (/, 07 0 25 68-33 20 100 65 98

CH ₁ CN (CH ₁ ), 99

(0.015) 22 10 10 10 100 11 Cl 0.017

CH ₁ OCH ₁ C (CHJ ₁ CH ₁ 100 6 100 100 100

(0.015) 22 10 0.017

101 26 22 100 100 45 100

(0.06) * 0 ', 07 0.0 95 22 0 100 22 100

102

table

I (continued)

formula

Application rate kg / ha (lb / A) Useful ² rw uu OT

WM Sn ΛΑ

% Damage weeds

HG KU PH NS COC VE TW % Control

* CH _:

⁽ 0.06 0.07 »20 10 10 21 10 21 45 54 40 54

CH ₁ CON = CCOCHsCH,

103

(0.015) 21 0.017

CH ₁ COCH (CH ₁ ),

104

0 10 10 100 14 53 100 100 55

GO-C

Cl 0

CH _a COCH, 105

⁽ 0.015 0.017 10 14 32 82 10 100 100 100 55

(0 015) 21 20 14 0.017

CH ₁ O (CH ₁ J ₁ CH, 106

14 20 100 100 40 55

table

I (continued)

formula

Applicable crops ² weeds

kg / ha Sg CN WH RI MG MU PW NS COC VE TW (Ib / A) % Damage% Control

(0.015) 45 21 22 0.017 100 45 100 100 100 100

(0.015) 21 0.017

CHCOCH, C = CH

108

10 11 50 40 26 100 100 100 100

(0.015) 0.017

CH ₁ OCNHCH (CH ₁ ), 109

10 20 10 11 75 40 100

CH ₁ CH ₁ OH

110

(0.015) 10 0 0 10 22 100 21 100 0.017

(0.015) 22 0.017

Il

CH ₁ CH ₁ OCSCH ₁ Ch ₁

111

2 0 10 88 100 100

T a b e 1

formula

Aiifbrincynenge Crops ²

weeds

kg / ha SB CN WH RI MG MU PW NS. COC VE TW (Ib / A)% Harmful% Control

(0.015) 20 0.017

Il

¹ CH ₁ CH ₁ OCO (CH ₁ ), CH ₁ 112

2 10 14 99 82 100

(0.015) 20 0.017

Il

CH ₁ CH ₁ OCNH (ChJ ₁ CH, 113

0 0 100 99 100 100

och:

114

115

(0.015) 20 0.017

22

100

(0.015) 21 10 19 11 19 98 100 38 0.017

(0.015) 14 10 6 0 100 6 100 100 0.017

CH ₁ CH ₁ OCH (CH ₁ ), 116

table

(Continuation)

formula

Applying crops ² weeds

kg / ha S8 CN WH RI HG MU PH NS COC VE TW (lb / A)% Damage% Combination ^^

CHCO ₁ CH ₁

CH,

117

• 0.015 * 11 10 11 10 100 11 40 100 - 100

οίοπ

(0.015) 1Ο 0, bi7

O O

CH ₁ CNHCh ₁ COCH,

10 11 35 11 O 85

118

(0.015) 21 0.017

119

0 14 22 11 100 100

Cl

CH,

(0.06)

ο; ο 7 0 0 0 10 10 74 32

ChHoN = CCO, CH ₁ CH,

CH,

120

(0.06) 0.07

20 0 0

CHCN CH »*

CH

40 100

121

Table I (continued)

formula

Application amount of crops ²

weeds

Ii cn wh rT mg hü pw ns cöc ve tw

(Ib / A)% Damage% Control

-Cl (0 0 , 06), 07 21 10 10 10 44 10 11 100 C-CN CH, 122 ►-C1 CH, O C -COCH (0 O, C = CH , 015), 017 10 0 0 0 95 62 100 100

CH, 123

100

100

(0.015) 0.017

0 10 100 96 100 100

C-COCH,

100

124

(0.06) 0.07

0 10 10 26 45 100

I (continued)

formula

crops

kg / ha SB CN WHRL (Ib / M% injury

weeds

KU PW NS COC VE% Combat

(0.06) 10 0 0 20 0 14 32 100 0.07

C-COCH (CH,), CH.

65

127

© .06) 22 0 0.07

11 10 45 32 100 100

100. -

¹ crop: SB = soybeans CN = corn WH = wheat Rl = rice.

Weeds: MG = funnel pasture MU = mustard PW = backward curved foxtail COC = pointed burp VE = grasswort TW = tea weed NS - nightshade

² The data indicate the percentage visual assessment of injury or control 14 days after treatment.

Example of use:

Table II shows the herbicidal activity of compositions of the present invention when applied to a variety of broadleaf weeds and grasses before emergence.

Table II.

Weed control / selectivity of selected C5-methylenilides towards crops.

formula

Application crops ² weeds

(10 / A) SB CO CN WH P) G VC CW TW PU COC ΓΤ BS LC

% Injury ³

% Combat

(0, W>) 2

0.56

Cl

CH ₁ OCH (CH ₁ ),

0 11 too 100 100 100 100 100 se ioo too

(o, so) 0 0.56

20 11 O 100 0 100 100 O 40 O 8C

Table II "(continuation)

Formula Aufbri

xngrnenge crops weeds

(lb / A) SB CO CN WH WG VE CW TW PW COC

% Damage ³ % control

0 O O O 82 100 20 100 100 O 6 55 98

0.56

CH ₂ SCHjCH ₁

(0.50) OO O O 100 40 100 76 100 O 0 0 0

0.56

ρ ι

CH ₁ OCH ₂ CO ₁ - ^ J

39

(0.25) O O O O 75 100 100 82 100 2 6 80 99

0.28

O CH ₁ OCH ₁ CH,

11

T a b e 1 le II (continued)

Foniel Plants ¹ Crops ² Weeds

kg / ha (IB / A) SB CO CM WH WG PU CW TV PW COC fT BS LC

% Damage ³ % control

(0.50) 0 0 0 0 0 77 »♦ 64 100 0 0 6 77

0.56

(0.50) 0

0.56

0 0 0 30 94 100 98 JOO 2 7b 50 99

P I

19

(0.25) 0

0.28

Cl CH ₁ OCH,

(0.25) 0 0.28

0 0 0 6 100 72 100 100 0 0 100

6 0 0 100 100 100 100 100 0 86 100

(0.50) 0 0.28

0 0 10 71 100 100 100 100 76 12 100

28

rabelle Il (l-setting)

- ιυ / - ^ o / S / 3

Fccnel arable land crops

weeds

SB CO CN WH MG VE CW TW PH COC FT BS LC (Ib / A) % Damage ³ % Control

⁽ 0.50> 00 0 0 0 26 0 22 86 0006

0.56 -

(0.50 0 0 0 0 0 0 100 100 100 56 100 90 100

o; 56

(0.5 °) 0 0 0 0 100 6 100 62 100 0 00 2

CH.OCHjCOCH.CH,

42

2 0 0 100 12 100 100 100 0 88 35 100

"CH ₁ SCH (CH ₁ ),

44

(0.25)

0.28

CH ₁ OCh ₁ CO -Cy

0 0 0 97 6 100 66 100 12 6 0 6

46

(0.50)

0.56

0 0 0 90 100 100 40 99 0 0 0 6

CH ₁ OCh ₁ COCH ₁ C = CH

55

Fconel

table

II (continued)

ncpenge SB Useful ² HG weeds COC FT BS LC kg / ha (Ibm) 0 CO CN WH% damage ³ 100 VE CW TW PW% Combat 94 6 0 42 (0.50) 0.56 0 N 20 0 0 100 100 86 100

CH _i 0CH _i C0CH {CH _{| i}

56

0,50) 0 ^T , 56

6 2 0 0 12 100 100 99 100 0 56 0 99

0 ι

CH ₁ NCH ₁ COCh ₁ CH,

CH.

59

(0.50) 12 0.56

0 0 100 100 100 100 100 62 100 32 100

98 0 0 86 11 100 100 100 - 26 0 55

_ / ^0CHC0 * ^CH P ¹ »

62

table II (continued)

weeds

Fornel application ¹ crop ²

kg / ha "cos ccn wht mg y c c tm pw coc ft bs lc

(lb / A) % damage ³ % control

(0.25) 2 0 0 0.28

CH ₁ OCH ₁

65

6 0 100 86 88 72 71 0 100

(0.25) 0.28

CH _S P

67

0 0 86 100 100 100 100 - 42 98 100

(0.25) _C1 0.28

6S

CH ₁ OC "I

CH. 0 0 74 0 50 77 45 100 100 100 74 56 100

0 0 50 99 100 100 100 0 74 2 56

78

i 0

CH ₁ OCNH (CHj ₁ CH,

(0.25) 0 Ο ', 28 0 0 71 100 20 100 100 0 0 0 98

CH ₁ OCO (CH ₁ CH,

79

(0.50) 0 20 0 54 30 100 51 100 98 100 76 0 100-0.56

ι ιυ - c \ iι y / o

Table II (port setting)

Formula Aufbriiignenge 'crops ² weeds

^{kg / ha} ~ S8 CO CN WH ~~ MG VE CH TW PW COC FT BS LC ( lb / A) % Damage ³ % Clogging

0 0 0 100 78 100 100 100 30 0 0 30

CH,

CH ₁ ON ^ CCOCH ₁ CH, II

81

(0.25) (/, 28

CH ₁ OCH (CH ₁ ), 139

(0.25) 0.28

0 56 0 0 42 0 12 88 100 0 0 30 50 0 0 0 0 72 86 61 100 100 35 56 6 100

CH ₄ OCschjCH,

87

0 2 0 0 82 100 77 100 100 42 30 0 97

CH ₁ OCNH (CH ₁ ), CH ₁

88

CO-C

(0,25) Cl ° ^'28

0 0 0 10 96 100 63 100 100 10 0 19 100

CH ₁ CN

96

0 0 0 10 70 7S 0 100 100 0 0 0 100

H ₂ OH

- -τη- Zb / t> 73

The amounts indicated are each based on the active ingredient.

¹ True Pre-Run Treatment: Sancings of the plants and weeds to be tested were sown about 2.5 cm below the surface. The soil was sprayed with a 1: 1 acetone: water solution of the test compounds.

² crops: SB = soybeans CO = cotton CN = corn WH = wheat

Weeds: MG = Morning Glory VE = HelleboreCW = Coffee Weed PW = Curved Foxtail COC = Spitzcloth FT = Foxtail BS = Broadleaf Signalgrass LC = Large Cinquefoil TW = Tea Weed

³ The data indicate the percentage visual assessment of injury 21 days after treatment.

Of course, the plant species used in the above experiments are only representative of a variety of plants that can be controlled by the compounds of the invention. The agents covered by the invention can be applied as postemergent and as preemergence herbicides by known methods. These agents will usually additionally contain a carrier and / or diluent, either liquid or solid

Suitable liquid diluents or carriers include water, petroleum distillates or other liquid carriers with or without surfactants. Liquid concentrates may be prepared by dissolving one of these compounds in a non-phytotoxic solvent such as acetone, xylene or nitrobenzene and dispersing the active ingredient in water with

Use of suitable surface-active emulsifying or dispersing agents.

The choice of dispersing and emulsifying agents and the amount applied are determined by the nature of the preparation and the ability of the dispersing and emulsifying agent to facilitate the dispersion of the compound. In general, it is beneficial to use as little dispersing and emulsifying agent as possible, in accordance with the desired dispersion of the compound in the spray, so that the rain does not re-emulate the compound after it has been applied to the plant, and from the Plant washes off. Nonionic, anionic amphoteric and cationic dispersing and emulsifying agents may be used, e.g. B. the condensation products of Alkyienoxiden with phenol and organic acids,

Alkylarylsulfonates, complex ether alcohols, quaternary ammonium compounds and the like.

In the preparation of wettable powders or dusts or granules, the active ingredient is dispersed in and on a correspondingly divided solid carrier such as clay, talc, bentonite, diatomaceous earth, fuller's earth and the like. In the preparation of the wettable powders, the above-mentioned dispersants and lignosulfonates may be added.

The required amount of the compound of interest may be applied in amounts of from 9.4 to 1871 l / ha (1 to 200 gallons per acre) of liquid carrier and / or diluent or in amounts of from 5.6 to 561 kg / ha {5 to 500 pounds per acre) inert solid carrier and / or diluent. The concentration is in the liquid concentrate

usually between about 10 and 95% by weight and for solid preparations at about 0.5 to about 90% by weight.

Satisfactory spray solutions, dusts or granules for a general application contain about 1.5 to 16.8 kg

Active ingredient / ha (Vi6 to 15 pounds per acre).

The herbicides contemplated by the present invention are highly safe (borderline safety) in that, when applied in an amount sufficient to control broadleaf weeds, they do not burn or damage the crops and are resistant to the weather, including rinse-off, decomposition by UV light, oxidation or hydrolysis in the presence of moisture or at least such decomposition, oxidation and hydrolysis which would significantly degrade or impart undesirable properties to the desired properties of the compound, e.g. B. phytotoxicity, is substantially reduced. It is understood that the compounds contained in the agents according to the invention also in combination with other biologically active compounds

can be used.

In the following Table III, the physical properties and the elemental analysis are in the inventive

Agents contained compounds indicated.

Table III (substituted methylene phenylimidic herbicide _P n Compound molecular formula

calculates C H

found C H

1 c, Λ , ClFNO ₄ F Cl H H 0 H -OCCH, > oil 58.04 4 30 3.98 2 C ₁ ,H, F Cl H H -OCH (CH .CH, 100-103 61.45 5 , " 3.98 3 C ₁ .H ₁ we f \\ j j F Cl H H -SCH ₁ CH oil 57,70 4 , 84 3.96 4 C ₁ ,H, , ClFNO ₄ S F Cl H H -SCH ₁ CO oil 54.34 4 , 31 3.52 5 C ₁ , CIFNO, F Cl H H -OH 133-138 58.17 4 , 23 4.52

C ₁₁ H ₁₄ Cl ₁ FNO ₁ SF Cl HH S - [VcI oil

F Cl H H

θ C ₁₁ H ₁₁ BrClFNO ₁ F CI H H Br 116 (d 9 C, .H ₁₁ ClFNO, F Cl H H ..-O 86-88 10 C ₁₁ H ₁₁ ClFNO, F Cl H H -OCH ₁ CH = CH ₁ oil 11 C ₁₁ H ₁₁ ClFNO ₁ F Cl H H -OCH ₁ CH, 94-96

57.54 4.57 3.80

61.89 5.67 3.75

57.47 5.01 3.77

53.81 4.43 3.45

58.32 4.31 4.45

58.08 3.25 3.23 57.14 3.74 3.06

60.99 5 _r 37 3.56 60.40 5.53 3.52

48 _r 35 3 _r 25 3.76 47.73 3.43 3.60

63.57 5 _f 60 3.71 63.40 5.66 4.07

61.80 4.90 4.00 61.48 4.92 4 _f 67

60.45 5.07 4.15 59.96 5.17 3.83

T a b e .1 Te IH (continued) Connection of empirical formula · »» ·

Mp CC)

calculates CHN

found C H N

12 C ₁₁ H ,, NO, H H H H -OH 110-115 70.02 5 _f 88 5.44 69.59 5.84 5.21   I • CO 13 C ₁₁ H , .CiNO, H Cl H H -OH η 121-124 61 _r 75 4 _r 84 4.80 62.03 4.81 4.58 ] I ro 14 C ,, H ,, CIFNO. F C) H H U -O-CCH ₁ CH, oil 59.10 4.68 3.83 58.43 4 _r 31 3 _f 73 cn cn 15 C ₁ , H ,, Cl ₁ NO, Cl CI H H -OH 138-140 55.23 4.02 4.29 55.34 3.93 4.01 16 C ₁ .H ₁ ,, CI ₁ NO, CI Cl H H -OCH (CH,), 120-123 58.71 5.20 3.80 57.95 5.00 3.73 17 C ₁ , H , .ClNO, H Cl H H -OCH (CH,), 120-121 64.77 6.04 64.89 6.03 4.06 18 C ₁ , H, ,, CIFNO, F Cl H H -OCH ₁ CH (CH ₁ ), 29-33 62.37 5 _r 79 3 _r 83 62.12 5.82 3.73 19 C ₁ , H ₁ ,, CIFNO, F Cl H H OCH, 93-95 59.36 4.67 4 _f 33 59 ^ 52 4.69 4 _r 18 20 C ₁₁ H ., ClF ₄ N ₁ O ₁ S F Cl H H * Ό -CF ₁ OSO, 173-174 48,42 3.29 5 _r 38 48.67 3.40 5 _r 23 21 C ₁₁ H , / IF ₁ NO, F Cl H H -F 132-135 57,80 3.88 4.49 57 _f 71 3 _r 56 4.60 22 C ₁ , H ,, CIF ₄ NO. F Cl H H υ Il -OCCF, 88-89 50.33 2.98 3.45 50 ^ 65 2.97 3.29 23 C ₁ .H ₁ , .FNO, F H H H -OCH (CH,), 97-99 68.12 6.35 4.41 68.32 6.26 4.47 24 Ct | H | .1F ₁ NO, F F H H -OH 119-120 61.43 4.47 4.77 60.96 4.58 4.80 25 C, .H ₁ ,, CIFNO, F Cl H H -OC (CH ₁ ), 131-134 62.28 5j79 3.83 62.73 5.83 3.80 26 C..H , .CIFN ₁ O ₁ F Cl H H -NHCH ₁ CeCH 80-88 62.34 4.65 8.08 59,60 4.65 7.48 27 Ct »Hj , .CIFN.O, F Cl H H -O 143-147 62.89 5.57 7.72 61.62 5.51 7.46 20 CH ₁ ,, CIFNO, F Cl H H -OCH ₁ C-CH 94-97 62.16 4.35 4.03 61.99 4.41 3.90 29 C, .H ₁ ,, NO, H H H H -OCH (CH,), 70-71 72.22 7.07 4 68 71.77 7.18 4.51

T abe T Te IH (continuation )

Compound formula ",

Fd CC)

calculates C H

found CH N

30 C ..H, .F ₁ NO, F F H H -OCH (CH ₁ ), 89-90 64.47 5.71 4.18 64,60 6.23 3.81, 31 C ,, H ₁₁ CIFNO ₁ p F Cl H H -S (CHJ ₁ CH, O Oil · 59.75 5.54 3.67 59.46 5.55 3.38 32 C ,, H ₁₁ ClFNO ₁ S F Cl H H -S (CHJ ₁ CH, ν- oil 57.35 5 _f 32 3.52 54.26 5.69 3.40 33 C ,, H ₁₁ ClFNO ₄ S F Cl H H -50, (CH ₁ J ₄ CH ο 132-135 55.14 5 _f 11 3.38 54.68 4.95 3.11 34 C ,, H ₁₄ ClFN ₁ O ₄ F Cl H H -C-NHCH, O 34-41 55.67 4.40 7.64 54 _; 81 4.48 7.40 35 C ,, H ₁₁ CIFNO, F Cl H H -oco-O O ^^ oil 59.79 5.02 3.32 58.87 5.08 3/56 36 C , .H..CIFN0. F Cl H H -OCCH (CHJ ₁ O oil 60.08 5.04 3.69 60.05 5JO 3.72 37 C , H ₁₁ CIFNO ₄ F Cl H H -OCC (CH ₁ ), 73-77 60.99 5.38 3.56 61.26 5.25 3.51 38 C ..H _i4 CIFN0, PS F Cl H H JUs (CH ₁ J ₁ CH> OCH, CH, Λ ,Oil 50.48 5.08 2.94 50.34 5.37 2.96 39 C ,, H ,, ClFNO ₁ F Cl H H -OCH ₁ COQ 84-86 60.62 5.32 3.21 60.70 5.36 3.32 40 C • Λ.ΒγΝΟ, H br H H OCH (CHJ, 110-112 57.14 5 _r 33 3, J0 57.23 5.71 3.50 41 C ,, H ₁₁ ClFNO, F Cl H H -0-φ 105-107 64.36 5.92 3.57 64.54 6.05 3.46 "2 C ,, ,, Ή ClFNO, F Cl H H -OCH ₁ CO ₁ CH ₁ CH, 98-101 57.65 4.84 3.54 57.87 4.61 3.58 43 C ,, H ₁₄ FNO, F H H H -OH oil 65.42 5.13 5.09 64.49 5.21 5.03 44 C ., H ,, CIFNO, S F Cl H H SCH (CHJ, 82.0-84.5 58 _f 77 5.21 3.81 58.23 5 _r 32 3.60 45 C ., 11,, CIFN ₁ O ₁ F CI H H ^CH V ~ \ Λ oil 65 _r 26 6.47 6.92 63.80 6.40 6.32 46 C ,, H ,, CIFNO, F CI H H U -OCILCO- ^ s) ' oil 61,40 5.56 3 _r 11 58.24 5.00 2.75

C ,, H ,, CIFNO ₄ F T ^R ' a b e 1 1 e III r I (Continuation calculates C H 5.02 N C found H N C ₁₁ H ₁₄ CIF ₄ NO ₁ F Cl .- <3 ¹ I CH, 59.10 3.60 3.83 58.78 5.01 3.79 C ₁₁ H ₁₁ CI ₁ FNO ₁ F Cl ^R · K CF, -NCH ₁ CO ₁ CH ₁ CH, CH, O -OCH-COCH ₁ CH ₁ CH, 0 -OC-C ¹ OCH ₁ CH, CH. CC) 52.12 4.33 3.58 52.17 3.82 3.33 Compound molecular formula C ₁₁ H ₁₁ CIF ₄ N ₁ O ₄ S F Cl H H -OCH ₅ CH ₁ Cl - oil 54.85 3.97 3.76 55.17 4.65 _3/44 47 Γ Η ΓIFMO ^ C Cl H H OCH, • CF.OSO, 95-97 51.83 4? Fi 2.63 49.31 4.21 48 lllfl C ₁₁ H ₁₁ CIF ₁ NO, Γ F ti H H -OCH ₁ CH, 94-97 fi? 7fi 3.36 ι m 49 C ₁₁ H ₁₁ ClFNO ₄ S F ν Ι Cl H H -o 229-233 Uc, / O 54.65 5.32 J _r 4NC 54.47 3.50 - 50 C ₁₁ H ₁₁ ClFNO, F Cl U U CH ₁ Co.-O oil 60.61 4.70 3.21 C] C ₁₁ H ₁₁ CIFNO, F Cl π H π F -F , CH, CH "CH KJ I 84-89 58,90 4.22 3.43 J · 52 C ,, H, _t CIFNO, F CI H H SCH, , CH ₁ C = CH oil 59.16 5.17 3.45 58.13 4.90 3.32 53 C ₁₁ H ₁₁ CIFNO ₁ F Cl H H -OCH ₁ CO , CH (CHJ ₁ , 51-54 58.61 5.32 3.42 59.20 4.31 3.36 54 C ₁₁ H ₁₁ ClFNO ₁ F Cl H H -OCH ₁ CO 106-110 69, A3 4.98 3.52 58.13 4.90 3.32 55 C ₁₁ H ₁₁ CIFN ₁ O ₄ CH ₁₁ CIFNO, C ₁₁ H ₁₁ CIFNO, F F F Cl H H -OCH ₁ CO CH, 102-104 68.66 5,42 5,17 5,47 3.64 56 Cl Cl Cl H H oil 58.75 58.61 59.50 6,85 3,42 3,30 68,40 5.06 3.69 57 H H oil 58.82 58.53 59.10 5.44 5.11 5.47 6.43 3.45 3.72 58 H H H H H H Oil oil oil 59 60 61

T a b e 1

HI (continued) Compound Formula "· ^R · ^R i

Mp CC)

calculates CH N

found CH N

62 C ,, H ,, CIFNO,

63 C ₁₁ H ₁₁ ClFNO.

64 C ₁₁ H ₁₁ ClFNO,

65 C,, H ,, CIFNO,

66 C ₁₁ H ₁₁ Cl ₁ FNO,

67 C ,, H "C1FN, O,

68 C ,, H ,, ClFNO,

69 C ₁₁ H ₁₁ CLEIN,

CH, F Cl HH -O- ^ OCHCO.CH.CH, 112-114 62.21 5.02 2 _f 79 61.36 5.11 2.59

F Cl H H

F Cl H H

F Cl H H F Cl H H F CI H H

-O

Cl H H -OCH-CO

68-72 58.75 5.66 2.54 58.76 5.53 3.92

71-74 58,75 5.66 2.54 58.61 5 _r 81 2.95

Cl H H

Oil 57.50 5.47

119-123 54.90 3.69

108-111 60.24 5.32

105-107 61.40 5.60

145.5-149.5 42.89 2.88

3.30

4.27

7.40

3.11

3.34

57.26 5.28 3.45 55.35 3.87 4.20 60.83 5, Al 7.13

60.77 5.60 2.60

C H

I "I

C ₁₁ H ₁₄ CIFN ₁ O ₄ C 1 H ₁₁ CIFN ₁ O ₄ C ,, M,, CI ₁ FN ₁ O ₁ S

F F F

F F

Cl H

Cl H

Cl H

Cl H

Cl H

H H H

H.H

 ΟΝΟ, O

-O-NH- (I)

-OCNH-C VcI

65-66 62.13 5.87

119-121 50.79 3.41

145-148 60.76 5.56

147-149 57.03 3.70

-0CNH- (3 ~ ^CI '17Ä-180 55,12 3,58

3.02

7.89

6.44

6.05

5.84

62.35 5.79 2.78

51.22 3.75 8.35

60.78 5.71 6.29

56.58 3.84 5.89

54.99 3.68 5.38

T a be 1 1

HI (continued)

Compound empirical formula ^R · ^R · ^R ip CC)

calculates C M

found CHN

C ,, H _lt CIFNO,

C ₁₄ H ₁₁ CIFNO,

C ₁ , H ₁₁ ClFN ₁ O,

C ₁₁ H ₁₁ ClFN ₁ O ₄

C ₁₁ H ₁₁ ClFNO,

C ₁₁ H ₁₁ ClFNO *

C ₁₁ H ₁₁ ClFN ₁ O ₁

C ,, H, CINO ₄

F F F H

Cl H H

Cl H H

Cl H

Cl H

Cl H

Cl H

Cl H ι

CH, H

OH OH »-OCH CH-CH.

HO OH -NHCH (CH ₁ ),

-OCNH (CHJ ₁ CH,

0 OCO (CH ₁ CH,

CH, -ON = CCO ₁ CH ₀ CH ₁

oil

oil

oil

oil

56.33 4 _f 99 56.31 5.32

87-90 61 _; 62 5.75

Oil 58.75 5.42

58.61 5.17 62.93 5.52

H -OCH (CH,),

73-76 56.81 4.77

114-116 68.25 5.96

3.65 52.83 4.87 3.47

2 _P 73 55.01 5.67 4.25

7.99 61.38 5.76 8.02

6,85 59,23 5,47 6,80

3.42 58.70 5.13 3.48

3.34 61.49 5.59 3.53

6.62 57.12 5.08 6.79

3.18 68.26 6.20 4.61

C ₁₁ H ₁₁ ClFN ₁ O ₄

C ₁₁ H ₁₄ BrNO,

C ₁₁ H ₁₁ ClFN ₁ O,

C, .H, ₄ BrNO,

F H F

Cl

Cl H

Br H

Cl H

H -NHC (CH ₁ J ₁ CO ₁ CH, 91-93, 58.75, 5.42 H -OH 108-110, 53.59, 4.20

Oil 59.92 5.82

H-NHCHCH ₁ OCH ₁

H Br HH ⁷ , ⁸ - ⁸⁰

6.85 58 55 5.77 " 59 I 4.17 53 66 4.41 H 21 I M cn vj 7.36 , »/ 37 5.77 3 / 60 cn • »j CO 3.03 56 84 5.60 13

table IH (continued)

Compound empirical formula ^R · ^R · ^R »

calculates CH N

found CH N

87 C ₁ , H ₁ , ClFNO ₄ S

88 C..H .ClFN _f, O, S

89 C ₁₁ H ₁₄ ClFN ₁ O ₄

90 C ,, H ,, CIFN ₁ O ₄

91 C ₁ , H ₁₁ ClFNO ₁ S

92 C ₁₁ H ₁₄ ClFN ₁ O ₁ S

93 C ^ H ₁₁ ClFN ₁ O ₁

94 C _lt H _lf CIFNO,

95 C ₁ H ₁₁ ClFNO ₄

F Cl H H O -OCSCH ₁ CH, oil S F Cl H H -OCNH (CHJ ₁ CH ₁ oil F Cl H H 0 -OCH ₁ CNH- ^ oil F Cl H H -NHCH ₁ CO ₁ CH ₁ CH, oil F Cl H H -Κ} oil F Cl H H -0-CNH - ^ s) oil F F Cl Cl H H H H - «« - Ο 0 0 -OCCH ₁ COCH ₁ CH ₁ 6 oil

F Cl H H54.34 4.31 3.52 53.95 4.34 4 _f 02 56.53 5.22 6,59 56,11 5,59 6,53

60,20 5,71 5,87 56,63 5,22 6,84

60.76 5.56 6.44

57.80 5,11 7,10

60.96 5.37 3.56

58.59 5.36 6.21

68-70 63.74 5.89 7.43 63.46 5.73 7.26 56

, 68 4.52 _3/31 57.12 4.60 3.58

62.15 5.22 3.45 62.14 5.38 3.22

96 CH ₁₁ CIFN ₁ O, 'F Cl HH -CN

97 C ₁ , H ₁₄ ClFN ₁ O, 98 C ₁ , H ₁ , CIFNO ₄

99 C ₁₁ H ₁₁ ClFN ₁ O ₁

100 C ₁ , H ,, ClFNO ₄

F CI H H -COCH ₁ C = CH 100-103 61.99 5.95 6.89 F Cl H H 9 -CN (CHJ 10 ₎ 98-100 60.73 4.02 3.73 F Cl H H It -OCH ₁ C (CH ₁ ), CH, 186-188 59.26 4.97 7.68 F Cl H H oil 59 50 5.47 3.30

144-147 60.29 3.80 8.79 60.33 4.09 8.79

61.08 5.82 6.49 60.53 4.33 3.60

57.51 4.95 7.25 59.57 5.75 4 _; 09

table

III (continued)

Connection of empirical formula "" "· CC)

calculates C H

^ found C H

101 C ₁₁ H ₁₁ CIFN ₁ O ₁ S

^{102 c} .. ^{H,. CIFN} i ° 4

103 C ₁₁ H ₁₁ CIFN ₁ O,

104 C ₁ , H ,, ClFNO ₄

105 C ,, H ,, C1FNO ₄

F F F F

Cl H

Cl H

Cl H

Cl H

F Cl H

H H H H H

114-116 57,79 5,11

'172-174 59 _f 04 4.96

-CON = CCOjCH ₁ CH ₃ 42-45 55.94 4.47 0

-COCH (CHJ, 81-82 60.08 5.04

113-115 58.04 4.30

7.09 57.51 5.12 6.98

0 CH,

-COCH ₁

6.88

3.69

59 _f 32 5.42 6.80

6.2t 56.05 4.89 5.88

60.53 5.21 3.52

3.89 58 _; 06 4.51 3.49

106 C _It H ,, CIFNO,

107 C ₁₁ H ₁₁ ClFNO ₄

108 C ₁₁ H ₁₁ CIFNO ₄

109 CH 1 ClFN ₁ O *

F F F F

CI H

Cl H

Ci H

Cl H

H -O (CH ₁ J ₁ CH,

Oil 62.38 5.79 3.83 62.48 5.94 3.75 Oil 62.93 5.52 3.33, 62.88 5.89 3.18 Oil 61.62 4.40 3.59 61 , 15 4.94 3.68

CH, -C-O

0 CH, -COCH ₁ C = CH

0 H -OCNHCH (CHJ, 109-111, 57.80, 5.11, 7.10, 57.98, 5.35, 7.39

110 C ₁ , H ₁ , CIFNO,

111 C ,, M _lt CIFNO ₄ S

112 C ₁₁ H ₁₁ ClFNO,

F Cl H H59.36 4.67

F Cl H

F Cl H

113 C ₁₁ H ₁₄ ClFN ₁ O ₄ .F Cl H

55.41 4 _; 65

-CH ₁ OH oil

η ..

-CH ₁ OCSCH ₁ CH ₁ 01

-CH ₁ OCO (CHJ ₁ CH, oil 59.50, 5.47

-CH ₁ OCNH (CHJ ₁ Ch; 95.0-'96.5 59.64 5.72

4.32 59 _; 45 5.17 4.06

3.40 55.25 4.95 3.38

3.30 58.23 5.45 3.27

6,62 59,85 5,90 6,70

table III (continued)

Connection Surnnenformel ^R » ^R · ^R » ^R *

calculates CHN

found

Il

IH C ₁₁ H ₁₄ ClFN ₁ O ₁ SF Cl HH -CH ₁ OCNH (CHj ₁ CH, ΟΊ

5.51, 6.38, 57.65, 5.59, 6.28

115 CH ₁₄ ClFN ₁ O, 116 CH ₁₁ ClFNO,

118C ,, H, JCIFN.O,

119 C ^ H ₁₁ ClFNO ₄

120 C ₁₁ H ₁₁ ClFN ₁ O,

121 C..H, ClFN ₁ O,

122 C ₁₁ H ^ CIFN ₁ O ₁

123 C ₁₁ H ,, CIFNO ₄

124 C ₁₁ H ^ CIFNO,

125 C ₁₁ H ₁₄ CIFN ₁ O.

126 CH ₁₀ ClFN ₁ O,

F Cl H CH, -CN

F Cl HH -CH ₁ OCH (CH ₁ ),

F F F F F F F F

Cl H CH ₁ -CO ₁ CH,

Cl HH -CNHCH ₁ CO ₁ CH,

0 Cl H is CH, -COCH (CH,),

0 CH, Cl H CH, -CON = (XO ₁ CH ₁ CH,

0 Cl H CH, -Un (CH ₁ ),

Cl is CH, CH, -CN

0 Cl CH, CH, -COCH ₁ C = CH

0 Cl CH, CH, -COCH,

0 CH, Cl CH, CH, -CON = C ¹ CO ₁ CH ₁ CH,

F Cl H H

57-60 61 _r 36 4 _; 24 8,42 61,73 4,69 7,95 46-48 62,38 5,79 3,83 61,34 5,80 3,85

59.11 4.69 3.83 _58/87 5.05 3.80

206-209 55,82 4,44 6,85 54,99 4,35 6,77 100-103 60,99 5,38 3,56 60,76 5,48 3 _; 59

56 _f 84 4.77 6.03 55.85 5.09 6.12

54-57 60.24 5.32 7.39 59.93 5.44 7.31

167-169 62.34 4.65 8.08 61.09 4.80 7.75

97-100 62.46 4.74 3.47 60.58 4.57 3.15

71-74 60.08 5.04 3.69 59.68 5.19 3.63

70-73 57 _; 68 5.05 5.85 57 ^ 77 5.18 5.78 61.43 5.16 7.17

^T e e 1 1 e in (continued)

Compound Compound R, R _e R, R ₄ ¥ F p calculated found

"_ TC) CHM CHW

0 127 C ₁ H ₁₁ CIFNO ₄ F Cl CH, CH, -COCH (CH,), 159-161 61 _f 82 5.68 3.43

128 C _{l (} Hl ₍ CIFN, O _a F Cl H CH ₁ CH, -CN oil 62.30 4.65 8.07

Table III Physical properties of AniliH

Compound molecular formula structural formula

calculated found

CO CHN C HN

Ct _t H _t , CIFN, O ₄

Il

C-

α ^C "O / H, OCH (CH 2), C-92.0-94.5 60.20 6.43 6.38 60.65 6.44 6.23 ..

100-103 62.48 6.67 6.63 61.97 6.24 6.26

CH ₁₁ CIFNO ₁ p

58,77 5.21 3 _f 81 57.23 5 _; 26 3.95

0 CH ₁ OCH (CH 2),

C ^ H ₁₁ CIFNO,

OH F

145.0-146.5 61.10 5 _f 98 3 ^ 96 61.26 5.99 3.91

0 CH ₁ OCH (CH 2),

C ,, H ^ ClFNO ₄ .Na

C-ONa C-NH-V " ^N ) -Cl

Il

335 °

55 _r 03 5.39 3.57

CH ₁ OCH (CH ₁ ),

Compound molecular formula structural formula cc)

calculates CHN

found CHN

C ₁₁ H 1 ClFNOS ₁

C ,, H ,, C1FN, O,

C ₁₁ H ₁₄ ClFN ₁ O,

C _it H ,, CIFN ₁ O,

C ₁₁ H ^ CIFN ₁ O ₁

97-101 56.31 4.99 3.65 56.20 4.95 3.50

ti

C-NH (CHJ ₁ CH ₁

C-NH - / "* 158-160 62 ^ 18 7,12 6,59 61 _; 91 7,37 '6,66

ti 0

0, C-NHCH »

CH ₁ OCH (CH ₂ ),

α ¹ """" ¹ 'ρ C _NH -O-Cl

CH ₄ OCH (CH 2), 160.5-161.0 59 _r 60 6.32 7,32 59,11 6,23 7,06

Il

-NHCH, - ^ ' ^v \ Il F,

α: 151-152 65.42 6.15 6.11 65.36 6.51 5.84

C-NH

Il

H ₁ OCH (CH ₁ ),

C-NH

174-175 61 _r 68 6,41 6,85 61,13 6,91 6,65

CH ₁ OCH (CHJ ₁

Molecular formula table III (Continuation) N C found N connection structural formula Fp calculates CC) C H

C ₁ ^ ₁₁ CIFNO ₄

CH ₁ OCH (CHj ₁

60.68 5.86 3.54 60.29 5.65 3.55

C ₁₁ H ₁₁ ClFN ₁ O ₁

α-C-NH-pV C-NH- ^

-Cl

N o

150-152 64,99 7,20 9, .1O 64 _; 78 7.09 9.08

C ₁ , H ₁ , ClFNO ₄

C ₁₁ H ₁₁ CIFN ₁ O ₁

Il C-OCH,

C-NH - ^ _ 7-Cl

° CH ₁ OCH (CHJ,

N (CH ₁ CH,),

85-115 59.45 6.04 3.65 59.46 6 _; 09 3 _; 44

O CH ₁ OCH (CHJ ₁

64.61 7 _f 39 6.85 64.26 7.64 6.38

CH ₁₁ ClFNO ₁ S

O CH ₁ OCH (CHJ ₁

59.44 6.04 3.65 59.12 6.00 3.68

Claims (9)

- 1 - Δ.-3Ι oil O claims: A herbicidal composition, characterized in that it consists of an acceptable carrier and a herbicidally effective amount of a compound of the formula exists in the: RI and R ₂ independently of one another mean: Hydrogen, halogen, (C ₁ -C ₃ ) -alkyl, (C ₁ -Cs) -alkoxy, trifluoromethyl, Phenoxy or benzyloxy, where the phenyl ring may be substituted by halogen, (Ci-C ₃ ) alkyl, (Ci-C ₃ ) alkoxy, cyano, nitro, alkylthio or haloalkyl groups; R ₃ and R ₄ independently of one another are hydrogen, C ₁ -C ₈ -alkyl, alkenyl or alkynyl or halogen; Y contains not more than 10 aliphatic carbon atoms and means: Hydrogen, halogen, cyano, nitrate, C 1 -C 8 -alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, Cycloalkylalkyl, cycloalkenylalkyl, Hydroxy, alkoxy, alkenoloxy, alkynyloxy, cycloalkyloxy, cycloalkylalkoxy, cycloalkenyloxy, Hydroxyalkyl, alkoxyalkyl, alkenyloxyalkyl, alkynyloxyalkyl, cycloalkyloxyalkyl, C 1 -C ₈ -alkylthio, alkenylthio, alkynylthio, cycloalkylthio, cycloalkenylthio, alkenylthioalkylk, Alkenylthioalkyl, alkynylthioalkyl, Phenyl, phenoxy or phenylthio, wherein the phenyl ring may be substituted by one or more halogen atoms, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or Haloalkyl groups. Alkoxycarbonyl, cycloalkyloxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, alkoxycarbonylalkoxy, cycloalkyloxycarbonyloxy, alkenyloxycarbonylalkoxy, alkynyloxycarbonylalkoxy, alkoxycarbonyloxy, cycloalkyloxycarbonyloxy, Alkenylyloxycarbonyloxy, alkynyloxycarbonyloxy, alkylcarbonyl, cycloalkylcarbonyl, Alkenylcarbonyl, alkynylcarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, Alkenylcarbonylalkoxy, alkynylcarbonyloxy, alkylcarbonylalkoxy, cycloalkycarbonylalkoxy, alkenylcarbonylalkoxy, alkynylcarbonylalkoxy, alkylcarbonylalkyl, alkenylcarbonylalkyl, alkynylcarbonylalkyl, cycloalkylcarbonylalkyl, alkoxycarbonylalkyl, alkenyloxycarbonylalkyl, Alkynyloxycarbonylalkyl, cycloalkyloxycarbonylalkyl, alkylcarbonyloxyalkyl, alkenylcarbonyloxyalkyl, alkynylcarbonyloxyalkyl, cycloalkylcarbonyloxyalkyl, alkoxycarbonyloxyalkyl, alkenyloxycarbonyloxyalkyl, alkynyloxycarbonyloxyalkyl, Cycloalkyloxycarbonyloxyalkylfalkoxycarbonylalkylcarbonyloxy, haloalkylcarbonyloxy, haloalkoxy, alkoxyalkoxy, cyanoalkoxy, phenylcarbonyloxy, phenolxycarbonyloxy, Phenylcarbonylalkoxy, phenoxycarbonylalkoxy, phenylcarbonylalkylthio, Phenoxycarbonylalkylthio, where the phenyl ring may be substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl groups, alkoxycarbonylalkylthio, alkenyloxycarbonylalkylthio, alkynyloxycarbonylalkylthio, cycloalkyloxycarbonylalkylthio, alkylcarbonylalkylthio, alkenylcarbonylalkylthio, Alkynylcarbonylalkylthio, cycloalkylcarbonylalkylthio, alkylthioalkoxy, alkoxyalkylthio, alkylthioalkylthio, haloalkylthio, alkylsulfinyl, alkensulfinyl, alkynesulfinyl, cycloalkylsulfinyl, phenylsulfinyl, phenylsulfinyl substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl groups, alkylsulfonyl, alkenylsulfonyl, alkynylsulfonyl , Cycloalkylfonyl, phenylsulfonyl, phenylsulfonyl, substituted by halogen, lower alkyl Alkoxy, cyano, nitro or haloalkyl groups. Alkoxycarbonylalkylsulfinyl, alkenyloxycarbonylalkylsulfinyl, alkynyloxycarbonylalkylsulfinyl, Cycloalkyloxycarbonylalkylsulinyl, Alkylcarbonylsulfinyl, Alkenyicarbonylalkylsulfinyl, Alkinylcarbonylalkylsulfinyl, Cycloalkylcarbonylalkylsulfinyl, Alkoxycarbonylalkylsulfonyl, Alkenyloxycarbonylalkylsulfonnyl, Alkinyloxycarbonylalkylsulfonyl, Cycloalkyloxyarbonylalkylsulfony ^ Alkylcarbonylalkylsulfonyl, Alkenylcarbonylalkylsulfonyl, Alkinylcarbonylalkylsulfonyl, Cycloalkylcarbonylalkylsulfonyl, alkylthiocarbonyl, alkenylthiocarbonyl, Alkinylthiocarbonyl, Cycloalkylthiocarbonyl, phenylthiocarbonyl, phenylthiocarbonyl substituted by halogen, lower alkyl, lower alkoxy, cyano , Nitro, alkylthio or haloalkyl groups, Alkylthiocarbonyloxy, alkenylthiocarbonyloxy, alkynylthiocarbonyloxy, phenylthiocarbonyloxy substituted by halo, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or halo groups, alkylthiocarbonyloxyalkyl, alkenylthiocarbonyloxyalkyl, alkynylthiocarbonyloxyalkyl, cycloalkylthioarbonyloxyalkyl, phenylthiocarbonyloxyalkyl, phenylthiocarbonyloxyalkyl wherein the phenyl ring is substituted by halogen, lower one Alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl groups. Amino, aminocarbonyl, aminocarbonyloxy, aminothiocarbonyloxy, aminocarbonylalkoxy, aminocarbonyloxyalkyl, aminothiocarbonyloxyalkyl or aminocarbonylalkylthio, wherein (a) the amino group may each be substituted by up to 2 substituents independently selected from: alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkoxyalkyl, alkoxycarbonylalkyl, alkenyloxyalkyl, alkynyloxyalkyl, phenyl or phenyl substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkythio or haloalkyl groups, or (b) the amino group has two substituents which, together with the amino nitrogen, form a 5- or 6-membered heterocyclic ring containing 0-3 further heteroatoms selected in any combination of the group consisting of oxygen, nitrogen and sulfur, Aminocarbonylalkylamino wherein each of the amino groups may be independently substituted by 0 to 2 alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyalkyl, phenyl or phenyl substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl groups, in any combination, An aminocarbonylalkylamino wherein the terminal amino group has two substituents which, together with the terminal amino nitrogen, form a 5- or 6-membered ring containing 0-3 further heteroatoms selected in any combination of the group consisting of oxygen, nitrogen and sulfur . Alkylcarbonylalkylamino, alkoxycarbonylalkylamino, phenylcarbonylalkylamino and phenoxycarbonylalkylamino, where the amino group may each be substituted by an alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyalkyl, phenyl or phenyl substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl groups, phenylcarbonylalkylamino or phenoxycarbonylalkylamino wherein the amino group may each be substituted by an alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyalkyl, phenyl or phenyl substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or Haloalkyl groups, and the phenyl group may each be substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl groups, alkoxycarbonylalkylaminocarbonyl, wherein the amino group may be substituted by an alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyalkyl , Phenyl or phenyl substituted by halogen, niede R 1 is alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl groups, oximo, alkoxycarbonyloximino, alkoxycarbonyloximinocarbonyl, any 5- or 6-g lower heterocycle containing one to three oxygen, nitrogen or sulfur atoms, any the following functional groups: 0 0 , C-OR ₅ , ^CN , CR ₇ - C - R ₆ , - C - R ₆ , - C - R ₆ , \ - OR ₅ ^X S - ^0R 5 'S - ^0R 5 ö 0 0. -3- / LO / 0 / ύ ^CN CN C - NR ₈ R ₈ R ₉ - C - R. - O (CH ₂ ) n C - NR ₈ R _g (CH ₂ ) n -C -NRjRg  S-C-N , -S-C-N, -N-C-N '' R, R, - S (CH ₂ ) n C0 ₂ ^e Q® ^ "Λ χ® OCH ₉ CH - CH, ² ν ² - 0 (CH ₂ ) n H (R ₁₀ ) ₃ OCH ₂ CH - CH ₂ O 0 CH ₃ CH ₃ OCH ₂ CH - CH _? , OH OH - 0 - P - 0 - Pf J - 0 - POCH ₂ CH ₂ -N -OPS-CH-CH 2 CH ^{2 2} or-0-glycoside in which: R _{5 is} C ₁ -C ₆ alkyl, cycloalkyl, alkenyl, alkynyl or cycloalkenyl; R ₆ and R ₇ independently of one another are hydrogen, C ₁ -C ₆ -alkyl, cycloalkyl, alkenyl, alkynyl, cycloalkenyl, phenyl or phenyl substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl groups R ₈ and R _{9 is} hydrogen, C ₁ -C ₆ -alkyl, cycloalkyl, alkenyl, alkynyl or cycloalkenyl; η is an integer from 1 to 4; Q represents an alkali or alkaline earth metal cation or a cation derived from an inorganic or organic base; X is an anion derived from a strong acid, Ri ₀ Ci-C ₆ -alkyl, cycloalkyl, alkenyl or cycloalkenyl group; -O-glycoside is any sugar group bonded to the C ₅ methylene via a glycoside bond, the sugar being in the free hydroxyl form, or the sugar having free hydroxyl groups attached to protecting groups and being a heterocyclic ring system the phenyl ring is attached via a nitrogen atom which is also part of the ring system or a carbocyclic or heterocyclic ring system which is bonded to the ring via a nitrogen atom which is not part of the ring system. 2. Composition according to claim!, Characterized in that Z is- ¹ SC Qn is, wherein the individual substituents indicated there have the following meaning: A and A 'are independently oxygen, sulfur or NR; B and D are independently, oxygen, sulfur ^or-NR,: E halogen, hydroxyl, alkylcarbonyloxy, alkoxycarbonyloxy, alkylcarbonylthio, alkoxycarbonylthio, alkoxy, alkenyloxy, alkynyloxy, amino, alkylamino, dialkylamino, mercapto, alkylthio, alkenylthio, alkylsulphinyl or alkylsulphonyl, with with the proviso that E does not exceed 10 Contains carbon atoms, Ri is hydrogen, fluorine, chlorine or bromine, R _{2 is} fluorine, chlorine or bromine, R ₃ and R ₄ independently of one another are hydrogen or C ₁ -C ₃ -alkyl and R, R ₁₁ , R ₁₂ , R ₂ s and R ₂₆ independently hydrogen, alkyl alkylcarbonyl, alkenyl or alkynyl and Y is hydrogen, phenyl optionally substituted by C ₁ -C ₃ -alkylthio or haloalkyl groups, hydroxy, C ₁ -C ₁₈ -alkoxy, alkenyloxy, alkynyloxy or cycloalkoxy groups, phenoxy, optionally substituted by halogen, lower alkyl, lower alkoxy, cyano, Nitro, alkylthio or haloalkyl groups, C 1 -C 5 -alkylthio, phenylthio, phenylthio substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl groups, Alkoxycarbonylalkoxy, cycloalkoxycarbonylalkoxy, C 1 -C ₈ -alkylsulfonyl or alkylsulfonyl, alkoxycarbony- nialiamino or a five- or six-membered heterocyclic one to three oxygen, nitrogen or sulfur atoms in any combination containing ring. 3. Composition according to claim 1, characterized in that Z öS-- Ö W
A ' A ' and the individual substituents have the following meanings: A and A 'independently of one another, oxygen, sulfur or -NR; B and D are independently oxygen, sulfur or NR; E is halogen, hydroxy, alkylcarbonyloxy, alkoxycarbonyloxy, alkylcarbonylthio, alkoxycarbonylthio, alkoxy, alkenyloxy, alkynyloxy, amino, alkylamino, dialkylamino, mercapto, alkylthio, alkenylthio, alkylsulfinyl or alkylsulfonyl, with the proviso that E contains no more than carbon atoms G oxygen, nitrogen or sulfur in any oxidation state; R _{1 is} hydrogen, fluorine, chlorine or bromine,
R _{2 is} fluorine, chlorine or bromine, R ₃ and R ₄ independently of one another are hydrogen or C ₁ -C ₃ -alkyl and R, Ri ₃ -R ₁ O, R 23, R 24 and R ₂ 7 independently of one another are hydrogen, alkyl, alkylcarbonyl, alkenyl or alkynyl and Y is hydrogen, phenyl optionally substituted by C ₁ -C ₃ -alkylthio or haloalkyl groups, hydroxy, C ₁ -C ₁₈ -alkoxy, alkenyloxy, alkynyloxy or cycloalkoxy groups, phenoxy optionally substituted by halogen, lower alkyl, lower alkoxy, cyano , Nitro, alkylthio or haloalkyl groups, C 1 -C 5 -alkylthio, phenylthio, phenylthio substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkyithio, or haloalkyl groups, alkoxycarbonylalkoxy, cycloalkoxycarbonylalkoxy, C ₁ - C ₈ alkylsulfinyl or alkylsulfonyl, alkoxycarbonylalkylamino or a five- or six-membered heterocyclic ring containing one to three oxygen, nitrogen or sulfur atoms in any combination. 4. Composition according to claim!, Characterized in thatZ N- c *. VZ " is, wherein the individual substituents have the following meaning: A and A 'independently of one another oxygen, sulfur or -NR, B and D independently of one another oxygen, sulfur or -NR, R _{1 is} hydrogen, fluorine, chlorine or bromine, R _{2 is} fluorine, chlorine or bromine, R ₃ and R _{4 are} independently hydrogen or C ₁ -C ₃ alkyl and R, RI7-R2o, ^R22 / R28 and _R29 are independently hydrogen, alkyl, alkylcarbonyl, alkenyl or alkinyl and Y is hydrogen, phenyl optionally substituted by C 1 to C ₃ alkylthio or haloalkyl groups, Hydroxy, C ₁ -C ₁₈ -alkoxy, alkenyloxy, alkynyloxy or cycloalkoxy groups, phenoxy, optionally substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl groups, C ₁ -C ₈ -alkyl, phenylthio, phenylthio substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl, alkoxycarbonylalkoxy, Cycloalkoxycarbonylalkoxy, Cr-C ₈ alkylsulfinyl or alkylsulfonyl, alkoxycarbonylalkylamino, or a five- or six-membered heterocyclic one to three Oxygen, nitrogen or sulfur atoms in any combination containing ring. 5. Composition according to claim 1, characterized in that Z wherein the individual substituents have the following meaning: A and A 'are independently oxygen, sulfur or -NR, R is hydrogen, alkyl, alkylcarbonyl, alkenyl or alkynyl, R _{1 is} hydrogen, fluorine, chlorine or bromine, R _{2 is} fluorine, chlorine or bromine and R ₃ and R ₄ independently of one another are hydrogen or C ₁ -C ₃ -alkyl, R ₂ i is hydrogen, alkyl, alkylcarbonyl, alkenyl or alkynyl η is an integer from 0 to 2; and
Y is hydrogen, Phenyl, optionally substituted by C ₁ -C 8 -alkylthio or haloalkyl groups, hydroxy, C ₁ -C ₁₈ -alkoxy, alkenyloxy, alkynyloxy or cycloalkoxy groups, phenoxy, optionally substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro Alkylthio or Haiogenalkylgruppen, C ₁ -C ₈ -Al kylthio, phenylthio, phenylthio substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl, alkoxycarbonylalkoxy, Cycloalkoxycarbonylalkoxy, C ₁ -C ₈ -Alkylsulfinyl or alkylsulfonyl, alkoxycarbonylalkylamino or a five- or six-membered heterocyclic ring containing one to three oxygen, nitrogen or sulfur atoms in any combination. 6. Composition according to claim 1, characterized in that Z nc · QC '· ^ * ^ _ It -NH- is wherein the individual substituents have the following meaning: A and A 'independently of one another oxygen, sulfur or -NR, R is hydrogen, alkyl, alkylcarbonyl, alkenyl or alkynyl, R _{1 is} hydrogen, fluorine, chlorine or bromine, R _{2 is} fluorine, chlorine or bromine . R ₃ and R ₄ independently of one another denote hydrogen or C 1 -C ₃ -alkyl and J is hydroxyl or salts derived therefrom, alkoxy, alkenyloxy, alkynyloxy, amino substituted by up to two alkyl, alkenyl or alkynyl substituents, morpholino or pyrrolidino and Y Hydrogen, Phenyl, optionally substituted by C ₁ -C ₃ -alkyl, or haloalkyl groups, hydroxy, C ₁ -C ₁₈ -alkoxy, alkenyloxy, alkynyloxy or cycloalkoxy groups, phenoxy, optionally substituted by halogen, lower alkyl, lower alkoxy, cyano, Nitro, alkylthio or haloalkyl groups, C 1 -C 6 -alkylthio, phenylthio, phenylthio substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl groups, alkoxycarbonylalkoxy, cycloalkoxycarbonylalkoxy, Ci-Cs-alkylsulfinyl or Alkylsulfonyl, alkoxycarbonylalkylamino or a five- or six-membered heterocyclic ring containing one to three oxygen, nitrogen or sulfur atoms in any combination. 7. Composition according to claim!, Characterized in that Z is and the individual substituents have the following meaning: R _{1 is} hydrogen, fluorine, chlorine or bromine, R _{2 is} fluorine, chlorine or bromine, R ₃ and R _{4 are} independently hydrogen or C ₁ -C ₃ alkyl and
Y is hydrogen, Phenyl, optionally substituted by C ₁ -C ₃ -alkylthio or haloalkyl groups, hydroxy, C ₁ -C ₁₈ -alkoxy, alkenyloxy, alkynyloxy or cycloalkoxy groups, phenoxy, optionally substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro -, alkylthio or haloalkyl groups, C ^ Cs-alkylthio, phenylthio, phenylthio substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl, alkoxycarbonylalkoxy, cycloalkoxycarbonylalkoxy, d-Cs-alkylsulfinyl or alkylsulfonyl , Alkoxycarbonylalkylamino or a five- or six-membered heterocyclic ring containing one to three oxygen, nitrogen or sulfur atoms in any combination. 8. Composition according to claim 1, characterized in that Z is and the individual substituents have the following meaning: A and A 'independently of one another are oxygen, sulfur or -NR, R is hydrogen, alkyl, alkylcarbonyl, alkenyl or alkynyl, R 1 is hydrogen, fluorine, chlorine or bromine, R _{2 is} fluorine, chlorine or bromine and> R ₃ and R _{4 are} independently hydrogen or C ₁ -C ₃ -AIIc /! and Phenyl, optionally substituted by C ₁ -C ₃ -AHCyItHiO- or haloalkyl groups, hydroxy, C ₁ -C ₈ -alkoxy, alkenyloxy, alkynyloxy or cycloalkoxy groups, phenoxy, optionally substituted by halogen, lower alkyl, lower alkoxy, cyano, Nitro, alkylthio or haloalkyl groups, dCs-alkylthio, phenylthio, phenylthio substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl groups, alkoxycarbonylalkoxy, cycloalkoxycarbonylalkoxy, d-Ca-alkylsulfinyl or alkylsulfonyl, Alkoxycarbonylalkylamino or a five- or six-membered heterocyclic ring containing one to three oxygen, nitrogen or sulfur atoms in any combination. 9. Composition according to claim 1, characterized in that Z Ct> - is where the individual substituents have the following meaning: E chlorine, A and A 'are independently oxygen, sulfur or -NR, R is hydrogen, alkyl, alkylcarbonyl, alkenyl or alkynyl, R _{1 is} hydrogen, fluorine, chlorine or bromine, R _{2 is} fluorine, chlorine or bromine and R ₃ and R ₄ independently of one another are hydrogen or C ₁ -C ₃ -alkyl and Y is hydrogen, Phenyl, optionally substituted by C ₁ -C ₃ -alkylthio or haloalkyl groups, hydroxy, C ₁ -C ₁₈ -alkoxy, alkenyloxy, alkynyloxy or cycloalkoxy groups, phenoxy, optionally substituted by halogen, lower alkyl, lower alkoxy, cyano, Nitro, alkylthio or haloalkyl groups, C 1 -C 5 -alkylthio, phenylthio, phenylthio substituted by halogen, lower alkyl, lower alkoxy, cyano, nitro, alkylthio or haloalkyl groups, alkoxycarbonylalkoxy, cycloalkoxycarbonylalkoxy, C 1 -C ₈ -alkylsulfinyl or alkylsulfonyl, alkoxycarbonylalkylamino or a five- or six-membered heterocyclic ring containing one to three oxygen, nitrogen or sulfur atoms in any combination. 10. Composition according to claim 1, characterized in that Z   .... A 'is, where the individual substituents have the following meaning: A and A 'oxygen, R _{1 is} hydrogen, fluorine, chlorine or bromine, R _{2 is} fluorine, chlorine or bromine and R ₃ and R _{4 are} independently hydrogen or C ₁ -C ₃ alkyl and Y is hydrogen, Phenyl, optionally substituted by C ₁ -C ₃ -alkyl, or haloalkyl groups, hydroxy, C ₁ -C ₁₈ -alkoxy, alkenyloxy, alkynyloxy or cycloalkoxy groups, phenoxy, optionally substituted by halogen, lower alkyl, lower alkoxy, cyano, Nitro, alkylthio or haloalkyl groups, C ₁ -C ₈ -alkylthio, phenylthio, phenylthio substituted by halogen, lower alkyl, lower alkoxy, Cyano, nitro, alkylthio or haloalkyl groups, Alkoxycarbonylalkoxy, cycloalkoxycarbonylalkoxy, C 1 -C 6 alkylsulfinyl or alkylsulfonyl, alkoxycarbonylalkylamino or a five- or six-membered heterocyclic ring containing one to three oxygen, nitrogen or sulfur atoms in any combination.
11. Composition according to claim!, Characterized in that Z is where the individual substituents have the following meanings A and A 'oxygen, R _{1 is} hydrogen, fluorine, chlorine or bromine, R _{2 is} fluorine, chlorine or bromine and R ₃ and R _{4 are} independently hydrogen or C ₁ -C ₃ -alkyl and Y is hydrogen, Phenyl, optionally substituted by C ₁ -C ₃ -alkylthio- or haloalkyl groups, Hydroxy, C ₁ -C ₁₈ -alkoxy, alkenyloxy, alkynyloxy or cycloalkoxy groups Phenoxy, optionally substituted by halogen, lower alkyl, lower alkoxy, cyano, Nitro, alkylthio or haloalkyl groups, CH 3 alkylthio, phenylthio, phenylthio substituted by halogen, lower alkyl, lower alkoxy, Cyano, nitro, alkylthio or haloalkyl groups, alkoxycarbonylalkoxy, Cycloalkoxycarbonylalkoxy, C 1 -C 8 alkylsulfinyl or alkylsulfonyl, alkoxycarbonylalkylamino or a five to six-membered heterocyclic one to three oxygen, nitrogen or sulfur atoms in any combination containing ring. 12. Composition according to claim 1, characterized in that Z - NH- -J is where the individual substituents have the following meaning: A and A are oxygen, R _{1 is} hydrogen, fluorine, chlorine or bromine, R _{2 is} fluorine, chlorine or bromine and R ₃ and R _{4 are} independently hydrogen or C ₁ -C ₃ -A ^ yI and Y is hydrogen, Phenyl, optionally substituted by C ₁ -C ₃ -alkylthio- or haloalkyl groups, Hydroxy, C ₁ -C ₁₈ -alkoxy, alkenyloxy, alkynyloxy or cycloalkoxy groups, Phenoxy, optionally substituted by halogen, lower alkyl, lower alkoxy, cyano, Nitro, alkylthio or haloalkyl groups, C 1-6 alkylthio, phenylthio, phenylthio substituted by halogen, lower alkyl, lower alkoxy, Cyano, nitro, alkylthio or haloalkyl groups, alkoxycarbonylalkoxy, Cycloalkoxycarbonylalkoxy, C 1 -C 8 alkylsulfinyl or alkylsulfonyl, alkoxycarbonylalkylamino or a five- or six-membered heterocyclic one to three oxygen, nitrogen or sulfur atoms containing ring, J is hydroxy, alkoxy, alkenyloxy, alkynyloxy, amino substituted by up to two alkyl, alkenyl or alkynyl substituents, Morpholino or pyrrolidino. 13. Composition according to claim 1, characterized in that the active ingredient is N- (2-fluoro-4-chloro-5-isopropoxymethylene) phenyl] -3,4,5,6-tetrahydrophthalimide. 14. Composition according to claim 1, characterized in that the active ingredient is N- [2-fluoro-4-chloro-5- (cyclopentyloxycarbonylmethylenoxymethylenlphenyU-SAB ^ -tetrahydrophthalimide. 15. A composition according to claim 1, characterized in that the active ingredient is N- (2-fluoro-4-chloro-5-cyanomethylene) -phenyl-3,4,5,6-tetrahydrophthalimide. 16. Composition according to claim 1, characterized in that "the active ingredient is N- [2-fluoro-4-chloro-5- (ethylthiocarbonyloxymethylene) phenyl] -3A5,64etrahydrophthalimide. 17. A composition according to claim 1, characterized in that the active ingredient is N-2-fluoro-4-chloro-5- (n-butylaminocarbonyloxymethylenphenyl-SAB ^ -tetrahydrophthalimidist. 18. A composition according to claim 1, characterized in that the active ingredient is N-2-fluoro-4-chloro-5- (n butylaminothiocarbonyloxymethylenjphenyl-SAB ^ tetrahydrophthalimide. 19. Composition according to claim!, Characterized in that the active ingredient, N- [2-fluoro-4-chloro-5- (N-morpholinomethylene) phenyl] -3,4,5,6-tetrahydrophthalimide.