AP440A

AP440A - New substituted pyrazole derivatives, processes for their preparation and their use as herbicides.

Info

Publication number: AP440A
Application number: APAP/P/1993/000579A
Authority: AP
Inventors: Dorfmeister Gabriele Dr; Franke Helga Dr; Geisler Jens Dr; Hartfiel Uwe Dr; Bohner Jürgen Dr; Rees Richard Dr
Original assignee: Schering Ag
Priority date: 1992-10-12
Filing date: 1993-10-12
Publication date: 1995-12-14
Also published as: RO113244B1; WO1994008999A1; IL107231A; EP0663913B1; FI951722A0; DE69320050T2; KR100296062B1; FI951722A; DK0663913T3; AU5151393A; ES2122043T3; DZ1720A1; JPH08506086A; TW285634B; US5869686A; SK281874B6; AP9300579A0; KR950704312A; CN1060478C; ATE169017T1

Abstract

New substituted pyrazole derivatives of general formula

Description

Title: New substituted pyrazole derivatives, processes for their preparation and their use as herbicides

Field of the invention

This invention relates to new substituted pyrazole derivatives, their preparation, as well as intermediates, and their use as herbicides.

Prior Art

It is known that 1-phenylpyrazoles possess herbicidal activity (EP 154115).

However the herbicidal activity of these compounds in not high enough or selectivity problems can occur in important crops.

The object of the present invention is to make new compounds that have improved biological properties over the known compounds.

It has now been found that substituted pyrazole derivatives of general formula I

AiN/yn

N

(I) in which

R¹ is Cj-^-alkyl;

BAD ORIGINAL β

AP Ο Ο Ο 4 4 Ο

R² is C^C^alkyl, C₁-C₄-alkylthio, C^Ct-alkoxy, each of which is optionally substituted by one or more halogen atoms, or

R¹ and R² together form the group -(CH-,)_m;

R³ is hydrogen or halogen,

R⁴ is hydrogen or CpC^alkyl,

R⁵ is hydrogen, nitro, cyano or the groups -COOR⁷, -C(=X)NR⁷R⁸ or -C(=X)R¹⁰,

R⁶ is hydrogen, halogen, cyano, Cj-C^alkyl, (optionally substituted by one or more halogen or hydroxy groups), C_l-C₄-alkoxy, phenyl, (optionally substituted by one or more halogen, nitro, cyano, Cj-C^alkyl, C₁-C₄-alkoxy or halo-C_l-C₄-alkyl groups) , pyrrolyl, or is a (^-Cg-alkyl, C₃-C₈-alkenyl, C₃-C₈-alkynyl or Cj-Cg-alkoxy group, each of which is interrupted by one or more oxygen atoms, or is the group;

-(CH₂)_a-A, -(CH₂) _a-O- (CH₂)_b-R²², -(CH₂)_a-O-Rⁿ or -COR²⁴,

BAD ORIGINAL ft

AP 0 00 4 4 0

R⁷, R⁸ and R⁹, which may be the same or different, are hydrogen or C₁-C₄-alkyl or

R⁸ and R⁹ together with the nitrogen to which they are attached form a 5 or 6 membered saturated carbocyclic ring;

R¹⁰ is hydrogen or Cj-C₄-alkyl, optionally substituted by one or more halogen atoms,

R¹¹ is hydrogen, C^C^alkyl, C₂-C₆-alkenyl, C₃-C₆-alkynyl or phenyl (each of which is optionally substituted by one or more halogen atoms), C₃-C₈-cycloalkyl, cyanomethyl or the group R²¹CO-;

R¹² is C^-Cg-alkyl, C2-C6-alkenyl, C^-Cg-alkynyl or phenyl (each of which is optionally substituted by one or more halogen atoms), C3-C8-cycloalkyl, cyanomethyl, Cj-C^-alkoxy-C^-Cg-alkyl, di-Cj-C^-alkylaminoCj-C^alkyl, tetrahydrofurfurylmethyl, C3-C6-alkynyloxy-Cj-^-alkyl, benzyl, (optionally substituted by one or more halogen, nitro, cyano, Cj-c4-alkyl, Cj-^-alkoxy or halo-Cj-^-alkyl groups) , or is the group -C(=X)R²¹, - (CH2) _a-(0) _d-R²⁸, - (CH2) a-O-(CH2) b R²⁸ or - (CH2) _a-X-R³⁴, and when R⁵ is -C(=O)R¹⁰, and/or when R¹is Cj-^-alkyl, R² is difluoromethoxy, R³ is bromo and R⁵ is nitro or cyano, R¹² can also be hydrogen; or

R¹¹ and R¹² together with the nitrogen to which they are attached form a 3, 5 or 6 membered saturated carbocyclic or aromatic ring, in which a carbon atom is optionally substituted by an oxygen atom;

R¹³ is hydrogen, Cj-C^alkyl, C2-C6-alkenyl or C3-C6-alkynyl; or R¹³ and R¹⁴ together form the group -(CH2)_p;

R¹⁴ and R¹⁵, which may be the same or different, are

Cj-^-alkyl, C₂-C₆-alkenyl, C₃-C₆-alkynyl or phenyl (each of which is optionally substituted by one or more halogen atoms), hydrogen, C₃-C₆-cycloalkyl or the

BAD ORIGINAL &

AP Ο Ο Ο 4 4 Ο groups -XR¹⁸ or -NR¹⁹R²⁰;

R¹⁶ is hydrogen, Cj-C6-alkyl, C2-C6-alkenyl, Cj-C^-alkynyl, Cj-C^-alkylcarbonyl, cyano-Cj-^-alkyl, C1-C4-alkoxycarbonyl-Cl-C4-alky 1, di-C^-C^-alkoxy5 carbonyl-Cj-C^-alkyl, benzyl, C^-C^-alkoxyCj-C-alkynyl, or the group -(CH2)a-R³³, -(CH2)_a-X-R³⁰,

- (CH₂) _a-X- (CH₂) _b-R³⁰ or -(CH₂)_a-X-(CH₂)_b-X-(CH₂)_c-R³⁰,

R¹⁷ is hydrogen, Cj-C₄-alkyl, C₂-C₆-alkenyl, Cj-C^-alkynyl, cyano-C_l-C₃-alky 1, Cj-C^-alkylcarbonyl-Cj-C^-alkyl or phenyl,

R¹⁸ is Cj-^-alkyl, optionally substituted by one or more halogens;

R¹⁹ and R²⁰, which may be the same or different, are hydrogen or Cj-^-alkyl;

R²¹ is Cj-C₄-alkyl, (optionally substituted by one or more halogens) , Cj-C^alkoxy-Cj-Cq-alkyl, Cj-C₄-alkylthioCj-C₄-alkyl, C-j-C^cycloalkyl, phenyl, (optionally substituted by one or more halogen, nitro, cyano, Cj-C₄-alkyl, Cj-C^-alkoxy or halo-C^C^alkyl groups), or is the group -NR³¹R³² or - (CH₂) _a-(O) _d-R³³;

R²² is Cj-C^-alkoxycarbonyl or carboxy,

R²³ is chloromethyl, cyanomethyl, Cj-C₆-cycloalkyl (optionally interrupted by one or more oxygen atoms), or Cj-C₄-alkoxycarbonyl-C|-C₄-alkyl,

R²⁴ is hydroxy or the group -NR²⁵R²⁶;

A is -NR²⁵R²⁶ or -S(O)_n-R²⁷;

R²⁵ and R²⁶, which may be the same or different, are hydrogen or Cj-C₄-alkyl;

R²⁷ is Cj-^-alkyl, C₁-C₄-alkoxycarbonyl-Cj-C^-alkyl or carboxy,

R²⁸ is hydrogen, hydroxy, halogen, Cj-C^alkyl, (optionally substituted by one or more Cj-C₄-alkoxy groups), C₃-C₆-cycloalkyl (optionally interrupted by one or

BAD ORIGINAL

AP Ο 00 4 4 Ο more oxygen atoms and optionally substituted by dimethyl), furyl, thienyl or -C(=O)R²⁹;

R²⁹ and R³⁰, which may be the same or different, are CpC^alkyl or Cj-^-alkoxy;

R³¹ and R³², which may be the same or different, are

Cj-C₄-alkyl or phenyl;

R³³ is C₃-C₆-cycloalkyl (optionally interrupted by one or more oxygen atoms and optionally substituted by dimethyl), furyl, thienyl or -C(=O)R²⁹;

C 10 R³⁴ is Cj-C₄-alkyl;

a,	b	and c are 1, 2 or
d	is	0 or 1;
m	is	3 or 4;
P	is	2 or 3; and
X	is	oxygen or sulfur,

possess better herbicide properties than the known compounds of related structure.

Particularly active are those pyrazole derivatives as 20 defined above, in which

R¹ is methyl;

R² is methylthio or difluoromethoxy (and especially difluoromethoxy); or

R¹ and R² together form the group -(CH₂)₄;

R³ is hydrogen, chloro or bromo;

R⁴ is hydrogen;

R⁵ is hydrogen, nitro, cyano or -C(=X)R¹⁰.

In a particularly preferred group of compounds, R⁶ is 30 hydrogen, halogen, cyano, Cj-C^-alkyl, C_M-a lkylthio or

-NRⁿR¹², with R¹¹ and R¹² preferably being hydrogen, Cj^-alkyl or C_M-alkoxycarbonyl.

The term halogen means fluorine, chlorine, bromine and

BAD ORIGINAL ft _Ap 0 0 0 4 4 0 iodine.

It is to be understood that the term alkyl, alkenyl and alkynyl includes branched as well as straight chained hydrocarbon groups.

The invention also includes intermediates of general formula II

in which R¹, R² and R³ have the meanings given in general formula I, intermediates of general formula Ii

in which R^l and R² have the meanings given in general formula I, intermediates of general formula Ij

APOOO 4 4 Ο

bj).

in which R¹, R² and R⁵ have the meanings given in general formula I, intermediates of general formula Ik

(ik ) .

in which R^l, R² and R⁶ have the meanings given in general 20 formula I, intermediates of general formula II r’/Jn nh₂cn _(ij>_ in which R¹, R² and R³ have the meanings given in general formula I, and intermediates of general formula Im

BAD ORIGINAL ft

APOOOUO

ΝΑ \

\\ 'N !

R r⁶ C—NH_? ² (Ira ) in which R^l, R², R³ and R⁶ have the meanings given in general formula I.

The compounds of the invention of general formula I can be prepared, by a process in which

A) a compound of general formula II

R²

NHNH₂ in which R¹, R² and R³ have the meanings given in general formula I, is reacted with a compound of general formula III

Y CN in which R⁴ and R⁵ have the meanings given in general formula I and Y is C^-C^-alkoxy, hydroxy or halogen, or when R^s is hydrogen,

B) a compound of general formula II ,2

R'

RyVR' (ll).

NHNHN^:

badoriginal

AP Ο Ο Ο 4 4 Ο in which R¹, R² and R³ have the meanings given in general 5 formula I, is reacted with a 2-haloacrylonitrile of formula Ilia

CN

CH₂=C (Ilia),

Hal or with a 2,3-dihalopropionitrile of formula Illb

Hal—CH₂—CH

CN (Nib),

Hal in which Hal is halogen, or when R³ is halogen,

C) a compound of general formula Ia

N:

,N

R¹ R (la), in which R^l, R², R⁵, R¹¹ and R¹² have the meanings given in 30 general formula I, is reacted first with a halogenating agent to give a compound of formula lb

R

N R⁵

(Ib),

BAD ORIGINAL

AP 0 0 0 4 4 0 in which R^l, R², R^, R¹¹ and R¹² have the meanings given in general formula I, and Hal is halogen, and then further treated to give the desired compound, or when r5 is -C(=S)R¹⁰ and R⁶ is amino,

D) a compound of general formula Ic

(Ic), in which R¹, R², R³, R⁴ and R¹⁰ have the meanings given in general formula I, is treated with Lawesson's reagent, or when R³ is -OR¹⁶,

E) a compound of general formula Id

N— ,R

R, (Id),

Tr in which R¹, R², R³, R⁴ and R⁵ have the meanings given in general formula I, is first diazotised to give a compound of formula le

R;

N'

I

R' (le),

AP Ο Ο Ο 4 4 Ο ί

C in which R¹, R², R^J, R⁴ and R⁵ have the meanings given in general formula I, and then by heating to give a compound of formula If

in which R¹, R², R³, R⁴ and R⁵ have the meanings given in general formula I, which is then reacted with a compound of general formula IV

QR¹⁶ (IV) in which R¹⁶ has the meaning given in general formula I, and Q is a leaving group, or when R⁵ is nitro and R⁶ is -SR¹⁷,

F) a compound of general formula Ig

Λ

R^r

in which R¹, R², R³ and R⁴ have the meanings given in general formula I and Hal is halogen is reacted with a nucleophile of general formula V ^eSR¹⁷ (V) in which R¹' has the meaning given in general formula I, or when R⁵ is nitro and R⁶ is -S(O)_nR¹⁷, in which n is 1 or 2,

BAD ORIGINAL ft

AP Ο Ο Ο 4 4 Ο

G) a compound of general formula Ih 2

R‘ !

j=r

Ih),

NO, in which R¹, R~, R³, R⁴ and R¹⁷ have the meanings given in general formula I, is subjected to a stepwise oxidation with m-chloroperbenzoic acid, or when R⁵ is cyano H) a compound of general formula Ila

R-

NHNH.

(Ha), in which R¹ and R² have the meanings given in general formula I, is reacted with a compound of general formula IIIc

CN \

CN (IIIc), in which Y is Cj-Cg-alkoxy, hydroxy or halogen, or when R⁵ is nitro,

I) a compound of general formula Ii

R

(Ii)

NH₂ in which R^l and R² have the meanings given in general

BAD ORIGINAL ft

AP Ο Ο Ο 4 4 Ο formula I, is nitrated in known manner, or

J) a compound of general formula Ij / NtY

N ι 1 R (ij) in which R¹, R~ and R⁵ have the meanings given in general formula I, is brominated in known manner, or when when R⁵ is halogen,

K) a compound of general formula II

NHNH, (II) , in which R¹, R² and R³ have the meanings given in general formula I, is reacted with a compound of general formula IIIc /

CN

CN (H1_C) in which Y' is C₁-C₆-alkoxy, dimethylamino or halogen, to first give compound of formula II

( II) ,

BAD ORIGINAL &

AP Ο Ο Ο 4 4 Ο in which R¹, R² and R³ have the meanings given in general formula I, and this compound is then diazotised in known manner with sodium nitrite and converted to the corresponding halide, or

L) a compound of general formula Ik 2

R CN in which R^l, R² and R⁶ have the meanings given in general formula I, is treated with a halogenating agent, or

M) a compound of general formula Im

in which R^l, R² and R³ have the meanings given in general formula I, and R⁶ is y-C^-alkyl, (optionally substituted by one or more halogens) or is a C₂-C_g-alkyl, interrupted by one or more oxygens, is converted in known manner to the nitrile of general formula I, or when R⁶ is -NRⁿR¹²,

N) a compound of general formula In

APO 00 44 Ο in which R¹, R² and R³ have the meanings given in general formula I, is reacted with an amine in a solvent, or when R⁶ is -NRⁿR¹², in which R¹¹ is hydrogen and R¹² is C^Cg-alkyl,

O) a compound of general formula II N—

R³ // l !

\\

NH₂ cn (il) .

in which R¹, R² and R³ have the meanings given in general formula I, is reacted with a trialkyl ortho ester and then reduced, or

P) a compound of general formula Io <*· c

CN flo ) , in which R¹, R² and R³ have the meanings given in general formula I, and R¹² is Cj-C^-alkyl is reacted with an base and an alkylating agent or an acid chloride, or when R⁶ is -NRⁿR¹², in which R¹¹ and R¹² are Cj-Cg-alkyl,

Q) a compound of general formula II

R·

N:

N

NH₂ cn // (il)

BAD ORIGINAL ft

AP Ο Ο Ο 4 4 Ο in which R¹, R² and R² have the meanings given in general formula I, is reacted with approximately 2 mole of base and 2 mole of a suitable alkylating agent, or

R) a compound of general formula II Nz=r \\ ! \ NH₂ CN (II), in which R¹, R² and R² have the meanings given in general formula I, is reacted with or without a base and a suitable acid chloride, or

S) a compound of general formula Ip N— \ ( Ip ) ,

NH C = O

CN in which R¹, R², R² and R²¹ have the meanings given in general formula I, is reacted with a base and a suitable alkylating agent, or

T) a compound of general formula In

( In ) ’

R m which R , R and R^J have the meanings given in general formula I and R⁵ is cyano or nitro, is reacted with

BAD ORIGINAL ft

AP Ο Ο Ο 4 4 Ο an oxygen, nitrogen, sulfur or carbon nucleophile, or when

R⁶ is substituted methyl

U) a compound of general formula Iq

(i q), in which R¹, R², R³, R⁴ and R⁵ have the meanings given in general formula I, is reacted with a Lewis acid, or

V) a compound of general formula Ir

I 1 in which R¹, R², R³, R⁴ and R⁵ have the meanings given in general formula I, is treated with a halogenating agent, or

W) a compound of general formula Is

(I s),

BAD ORIGINAL ft

AP Ο Ο Ο 4 4 Ο in which R¹, R², R³, R⁴ and R⁵ have the meanings given in general formula I, is reacted with an oxygen, nitrogen, sulfur or carbon nucleophile, or when R⁶ is mercapto

X) a compound of general formula It

(I t)_; in which R¹, R², R³ and R⁴ have the meanings given in general formula I, is treated with sodium hydrogen sulfide, or

Y) a compound of general formula lu

(I U), in which R¹, R², R³ and R⁴ have the meanings given in general formula I, is treated with a suitable alkylating agent, or

Z) a compound of general formula Iv

(I v)

BAD ORIGINAL ft

AP Ο Ο Ο 4 4 Ο in which R¹, R², R³ and R⁴ have the meanings given in general formula I, and R^x is C^Cj-alkyl, is oxidised in stages.

The compounds of the invention of general formula I, in which R⁵ is nitro and R⁶ is halogen, can also be prepared according to the process described in DE 3501323.

The compounds of the invention of general formula I, in O 10 which R⁵ is the group -C(O)R¹⁰ and R⁶ is amino, can also be prepared according to the process described in Collect. Czech. Chem. Commun. 55., 1038-48 (1990).

The compounds of the invention of general formula I, in which R⁶ is the group -NRⁿR¹², can also be prepared according to the known processes described in DE 3 707 686, DE 3 543 034, EP 224 831, DE 3 543 035, JP 57167972 and DE 2 747 531.

The compounds of the invention of general formula I, in which R¹⁴ is the group -OR¹⁸ or -NR¹⁹R²⁰, can be prepared from compounds of general formula I, in which R⁶ is amino according to the known processes described in Chem. Soc. Rev. 4., 231-50 (1975) and J. March, Advanced Organic

Chemistry, 1985, p. 370.

The compounds of the invention of general formula I, in which R⁵ is cyano or nitro and R⁶ is C₁-C₄-alkyl, can be prepared according to known processes (J. Heterocyclic

Chem. 24, 1669 (1987), ibid. 24, 739 (1987).

The reactions are suitably carried out by reacting the compounds of formulae II, Ila or III in a suitable solvent at a temperature between -30 and 150°C, preferably at room temperature.

BAD ORIGINAL d

AP000440

As halogenating agent there can be used for example sulfuryl chloride, sodium hypochlorite, N-chlorosuccinimide, N-bromosuccinimide, bromine or chlorine.

Leaving groups in process variant E are chloro or bromo.

The nitration in process variant I) is suitably carried out in known manner with nitric acid in acetic anhydride. The reaction temperature lies in the region of -10 to 140°C.

The process variant J) is suitably carried out in a solvent at a temperature of -20°C up to the boiling point of the solvent.

As brominating agent in process variant J) there can be used, for example N-bromosuccinimide or bromine.

The reaction of compounds of general formula II is suitably carried by the method described in J. March, Advanced Organic Chemistry, 1985. p. 647.

The process variant L) is generally carried out in a suitable solvent, preferably acetonitrile or dichloromethane, at a temperature of between -10°C and 80°C.

Process variant M) is generally carried out according to the method described in Tetrahedron Letters, 1977 p. 1813.

Process variant O) is generally carried out according to the known methods (J. March, Advanced Organic Chemistry, 1985. p. 798-800 and literature cited there).

BAD ORIGINAL

AP Ο Ο Ο 4 4 Ο

C ¹⁰

C ¹⁰ (

(

Suitable bases for process variants P), Q), R) and S) include for example alkali metal and alkaline earth metal hydroxides, sodium methanolate, alkali metal hydrides, alkali metal and alkaline earth metal carbonates, tertiary aliphatic and aromatic amines, such as triethylamine and pyridine as well as heterocyclic bases.

Process variant T) is generally carried out for example according to methods described in J. Heterocyclic Chem.

25, 555 (1988).

The preparation can be carried out with or without a solvent. Should need arise, such solvent or diluents can be used which are inert to the reactants. Examples of such solvents or diluents are aliphatic, alicyclic and aromatic hydrocarbons, each of which can be optionally chlorinated, such as for example hexane, cyclohexane, petroleum ether, naphtha, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene dichloride, trichloroethane and chlorobenzene, ethers, such as for example diethyl ether, methyl ethyl ether, methyl t-butyl ether, diisopropyl ether, dibutyl ether, dioxane and tetrahydrofuran, ketones, such as for example acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, nitriles, such as for example acetonitrile and propionitrile, alcohols, such as for example methanol, ethanol, isopropanol, butanol, tertbutanol, tert-amyl alcohol and ethylene glycol, esters, such as for example ethyl acetate and amyl acetate, amides, such as for example dimethylformamide and dimethylacetamide, sulfoxides, such as for example dimethyl sulfoxide and sulfones such as for example sulfolane, bases, such as for example pyridine and triethylamine, carboxylic acids such as for example acetic acid, and mineral acids such as for example sulfuric acid

BAD ORIGINAL i

AP Ο Ο Ο 4 4 Ο and hydrochloric acid.

The compounds of the invention can be worked up in conventional manner. Purification can be achieved by crystallisation or column chromatography.

The compounds of the invention are, as a rule, colourless or slightly yellow crystalline or liquids or substances that are highly soluble in halogenated hydrocarbons, such as methylene chloride or chloroform, Ethers, such as diethyl ether or tetrahydrofuran, alcohols, such as methanol or ethanol, ketones, such as acetone or butanone, amides, such as dimethylformamide, and also sulfoxides, such as dimethyl sulfoxide.

The intermediate compounds of general formula II

(H).

in which R¹, R² and R³ have the meanings given in general formula I can be prepared in known manner (e.g. JP 62158260) from compounds of general formula VI

R' ^N=\

NH.

(VI ) in which R¹, R² and R³ have the meanings given in general formula I.

BAD ORIGINAL ft

AP Ο Ο Ο 4 4 Ο

The compounds of general formula II in which R¹ and R²together form the group -(CH₂)_m- and R³ is hydrogen, can be prepared by treating a compound of general formula Illc i| ⁰ ⁵ HalCH₃(Cr^)₃ — C-C=( (IHc), a

with hydrazine with addition of a base. The compound of general formula IIIc can be prepared by reacting a compound of general formula Hid 0

HalCtyCH^-C/ (III^d), a

and a 1,1-dihaloethylene.

The compounds of general formula VI, in which R¹ and R²have the meanings given in general formula I and R³ is halogen, can be prepared by reacting a compound of general formula VI in which R³ is hydrogen, with a halogenating agent.

The compounds used as starting materials for compounds of general formula VI, are of general formula VII

R²

(VH), in which R¹ has the meaning given in general formula I, and can be prepared for example, by a process in which, in the case when R² is C_t-C₄-alkyl, optionally substituted by

BAD ORIGINAL

AP Ο Ο Ο 4 4 Ο

Γ ίο ( .

( halogen,

a) a compound of general formula VIII, Villa or IX

R² y=\ (viii), NH₂ CN (Villa), // \ CX),

O CN in which R² is C|-C₄-alkyl, optionally substituted by halogen, is reacted with a compound of general formula X

R¹ - NHNH2 (X) in which R¹ has the meaning given in general formula I, optionally in the presence of a solvent, or when R² is Cj-C^-alkylthio, optionally substituted by one or more halogens,

b) a compound of general formula XI

in which R³⁵ is cyano or the group -COOR³⁶, in which R³⁶ is Cj-C^-alkyl, is reacted with a compound of general formula X, optionally in the presence of a solvent, e.g. water, to give first a compound of general formula XII

SH

N=J nh₂ (XII) ,

BAD ORIGINAL ft

AP Ο Ο Ο 4 4 Ο in which R¹ has the meaning given in general formula I and R³⁵ has the meaning given above, which is then reacted with a compound of general formula XIII

R³⁷Q (XIII) in which R³⁷ is CpCj-alkyl, optionally substituted by one or more halogens, and Q is a leaving group, and the resulting compound of general formula XIV

SR

-N

N· (XIV)

NH, is saponified and decarboxylated according to known literature methods (e.g. Zeitschrift fur Chemie 420, (1968)), or

c) a compound of general formula XV

C (XV).

SR CN 25 in which R³⁵ is cyano or the group -COOR³⁶, in which R³⁶ is C₁-C₄-alkyl, and R³⁷ is Cj-^-alkyl, optionally substituted by one or more halogens, is reacted with a compound of general formula X, optionally in the presence of a solvent, e.g. water, to give a compound of general formula XIV, or when R² is Cj-C^-alkoxy, optionally substituted by one or more halogens

d) a compound of general formula XVI

BAD ORIGINAL ft

APOOO440

(XVI), in which R¹ has the meaning given in general formula I, is 10 reacted with a compound of general formula XIII, in the presence of a base, or

h) a compound of general formula XVII ,CO₂Z

HO

Ν' ii ,N (XVII), in which R¹ has the meaning given in general formula I and Z is c^-C^-alkyl, is reacted, in the presence of a base, with a compound of general formula XIII

R³⁷Q (XIII) in which R³⁷ is Cj-C^-alkyl, optionally substituted by one or more halogens, and Q is a leaving group, and the resulting compound of general formula XVIII .CO,Z r^3/o

ΊΝ' R ¹ ,N (XVIII)_y in which R¹ has the meaning given in general formula I,

BAD ORIGINAL

AP Ο Ο Ο 4 4 Ο is Cj-C₄-alkyl, optionally substituted by one or more halogens, and Z is Cj-^-alkyl, is reacted with ammonia and the resulting compound of general formula XIX

II .GNH.

N' t

R ,N (X IX), in which R has the meaning given in general formula I and R³⁷ is Cj-C^-alkyl, optionally substituted by one or more halogens, is reacted with sodium hydroxide and a halogen, or when R³ in general formula I is halogen,

f) a compound of general formula XVIII or XIX r³'o

N'

Ϊ

R

II ,N

O

II ,C-NH.

CO₂Z (X IX), (XIII) in which R¹ has the meaning given in general formula I, R³⁷ is Cj-Cj-alkyl, optionally substituted by one or more halogens, and Z is Cj-C₄-alkyl, is reacted with a halogenating agent to give a compound of general formula XVIIIa and XlXb

Hal r'o

N'

I

R ,N .CO₂Z

Ha

II

-C-NH(XVI Ila) und

N R ¹ (X IXb)

BAD ORIGINAL ft

AP 0 0 0 4 4 0 in which R^l, R³⁷ and Z have the meanings given in general formula XVIII and XIX, or

g) a compound of general formula XIXa

Hal /C-NH₂-s :i l| ii 0 (XIXa), f?⁷o in which R¹ has the meaning given in general formula I, R³⁷is Cj-C₄-alkyl, optionally substituted by one or more halogens, and Hal is halogen, is reacted with sodium hydroxide and bromine to give a compound of general formula XX

(XX).

in which R¹, R³⁷ and Hal have the meanings given in formula XIXa, or when R¹ and R' together form a tri- or tetramethylene group

h) a compound of general formula XXI

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AP 0 0 0 4 4 0 in which n is 2 or 3, is reacted with hydrazine and the resulting 3(5)-amino-5(3)-hydroxyalkylpyrazole of general formula XXII

HO-(CH₂)_nCH

(XXII), in which n is 2 or 3, is reacted with hexane-2,5-dione, phthalic anhydride or tetrahydrophthalic anhydride, in a similar manner to known literature methods (Bull. Chem. Soc. Jp., 44 . 2856-8 (1971), or EP 305826), to give a compound of general formula XXIII

in which n is 2 or 3 and Q is an amino protecting group, such as e.g. Q_lz Q₂ or Q₃

and this is cyclised using the Mitsunobu variant (Synthesis, 1 (1981)), to give a compound of general

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AP Ο Ο Ο 4 4 Ο formula XXIV

(XXIV), in which η is 2 or 3, and then in the case when Q is Q₁₍this is treated with hydroxylamine as described in J. Org.

Chem., 49, 1224-1227 (1984), and in the case when Q is Q, or Q₃, this is treated with hydrazine, in a similar manner to known literature methods (Org. Synthesis, Coll. Vol.,

3., 148 (1955)).

The starting materials of general formula XXI can be prepared in known manner (Chem. Ber., 109(1), 253-60, 1976) .

(..

(

The compounds of general formula Ii, used as starting 20 materials, can be prepared by decarboxylating a compound of general formula XXV

in which R¹ and R² have the meanings given in general formula I.

The compounds of general formula XXV can be prepared by saponifying a compound of general formula XXVI

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AP Ο Ο Ο 4 4 Ο

in which R¹ and R², have the meanings given under general formula I and R⁷ is C_t-C₄-alkyl.

The compounds of general formula XXVI can be prepared by reacting a compound of general Ila, in which R¹ and R² have the meanings given under general formula I with a compound of general formula XXVII

CN

CO₂FT (XXVII), in which R⁷ is Cj-C₄-alkyl and Y is C^-Cg-alkoxy, hydroxy or halogen.

The intermediates of general formula Ij, can be prepared in an analogous way to process described above in which instead of the compounds of general formulae Ila and Ii the corresponding compounds of general formula XXVIII and/or XXIX

H NHNH₂

R

N (XXVIII)

(XXIX),

R

AP Ο Ο Ο 4 4 Ο

Vi.·.

are used.

The intermediates of general formula Ik, can be prepared by reacting a compound of general formula lib

R•N

N^: ./

NHNH, (H^b) in which R¹ and R² have the meanings given in general formula lib in an analogous way to processes described above.

The intermediates of general formula Im, in which R⁶ is Cj-Qj-alkyl, optionally substituted by one or more halogens or C₂-Cg-alkyl, interrupted by one or more oxygen atoms, can be prepared converting a compound of general formula Iq

( Iq ) , in which R¹, R² and R³ have the meanings given in general formula I, R⁶ is Cj-C₄-alkyl, optionally substituted by one or more halogens or C₂-C_s-alkyl, interrupted by one or more oxygen atoms, and R⁷ is Cj-C^alkyl, in known manner to the amide.

The compounds of general formula Iq can be prepared in known manner (J. Heterocyclic Chem 24., 1669 (1987), ibid.

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AP Ο Ο Ο 4 4 Ο

C ¹⁰ (

24, 739 (1987)).

The preparation of the intermediates can be carried out with or without a solvent. Should need arise, a solvent mentioned above can be used.

The named starting materials are either known in the or can be prepared in similar manner to known methods.

The compounds of the invention show a good herbicidal activity against broad leaved weeds and grasses. A selective use of the compounds of the invention in various crops is possible for example in rape, beet, soya beans, cotton, rice, barley, wheat and other cereals. Individual active substances are particularly suitable as selective herbicides in beet, cotton, soya, maize and cereals. However the compounds can be used for control of weeds in permanent crops, such as for example forestry, ornamental trees, fruit, vine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plantations.

The compounds of the invention can used for example against the following plant species:

Dicotyledonous weeds of the species: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Brassica, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Iponoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Lamium, Veronica, Abutilon, Datura, Viola, Galeopsis, Papaver, Centaurea and Chrysanthemum.

Monocotyledonous weeds of the species: Avena, Alopecurus,

Echinochloa, Setaria, Panicum, Digitaria, Poa, Eleusine,

Brachiaria, Lolium, Bromus, Cyperus, Agropyron,

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AP ο Ο Ο 4 4 Ο

Sagittaria, Monocharia, Fimbristylis, Eleocharis,

Ischaemum and Apera.

The rates of use vary depending on the manner of pre- and 5 postemergent use between 0.001 and 5 kg/ha.

The compounds of the invention can also be used as defoliants, desiccants and total herbicides.

The compounds of the invention can be used either alone or in admixture with one another or with other active agents. Optionally, other plant-protective agents or pesticides can be added, depending on the purpose for the treatment. When it is desired to broaden the spectrum of activity, other herbicides can also be added. Herbicidally active mixing partners suitable in this connection include for example, the active agents listed in Weed Abstracts, vol. 40, No. 1, 1991, under the heading Lists of common names and abbreviations employed for currently used herbicides and plant growth regulators in Weed Abstracts.

An improvement in the intensity and speed of action can be obtained, for example, by addition of suitable adjuvants, such as organic solvents, wetting agents and oils. Such additives may allow a decrease in the dose.

The designated active ingredients or their mixtures can suitably be used, for example, as powders, dusts, granules, solutions, emulsions or suspensions, with the addition of liquid and/or solid carriers and/or diluents and, optionally, binding, wetting, emulsifying and/or dispersing adjuvants.

Suitable liquid carriers are, for example aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene,

BAD ORIGINAL

AP Ο Ο Ο 4 4 Ο cyclohexanone, isophorone, dimethyl sulfoxide, dimethylformamide and other mineral-oil fractions and plant oils.

Suitable solid carriers include mineral earths, e.g. bentonite, silica gel, talcum, kaolin, attapulgite, limestone, silicic acid and plant products, e.g. flours.

As surface-active agents there can be used for example 10 calcium lignosulfonate, polyoxyethylenealkylphenyl ethers, naphthalenesulfonic acids and their salts, phenolsulfonic acids and their salts, formaldehyde condensates, fatty alcohol sulfates, as well as substituted benzenesulfonic acids and their salts.

The percentage of the active ingredient(s) in the various preparations can vary within wide limits. For example, the compositions can contain about 10 to 90 percent by weight active ingredients, and about 90 to 10 percent by weight liquid or solid carriers, as well as, optionally up to 20 percent by weight of surfactant.

The agents can be applied in customary fashion, for example with water as the carrier in spray mixture volumes of approximately 100 to 1,000 1/ha. The agents can be applied using low-volume or ultra-low-volume techniques or in the form of so-called microgranules.

The preparation of these formulations can be carried out in known manner, for example by milling or mixing processes. Optionally, individual components can be mixed just before use for example by the so-called commonly used tank-mixing method.

Formulations can be prepared, for example, from the

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AP Ο Ο Ο 4 4 Ο

C ¹⁰

C ¹⁰ (

( following ingredients.

A) Wettable Powder percent by weight active ingredient 35 percent by weight fuller⁷s earth percent by weight calcium lignosulfonate 2 percent by weight sodium salt of

N-methyl-N-oleyltaurine percent by weight silicic acid

B) Paste percent by weight active ingredient percent by weight sodium aluminium silicate 15 percent by weight cetyl polyglycol ether with 8 mole ethylene oxide percent by weight spindle oil percent by weight polyethylene glycol percent by weight water

C) Emulsifiable Concentrate percent by weight active ingredient percent by weight isophorone percent by weight of a mixture of the sodium salt of N-methyl-N-oleyltaurine and calcium lignosulfonate

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AP Ο Ο Ο 4 4 Ο

The following examples illustrate the preparation of compounds according to the invention.

Example 1.0

4-Acetvl-5-amino-l-(3-chloro-4,5,6,7-tetrahvdropyrazolo(1,5-a1pyridin-2-yl)pyrazole

0.56 g (3 mmol) 3-Chloro-2-hydrazino-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine was dissolved in 5 ml ethanol and ¢- 10 treated with 0.42 g (3 mmol) 2-ethoxymethylen-3-oxobutyronitrile. After heating under reflux for 3 hours, the mixture was concentrated and the residue purified by silica gel chromatography (hexane/ethyl acetate 1:1).

Yield: 0.75 g = 89.4% of theory mp: 153-154°C

Example 1.1

5-Amino-l-(3-chloro-4,5,6,7-tetrahydropyrazolo20 r1,5-aΊpyridin-2-y1)-4-thioacetylpyrazole

0.28 g (1 mmol) 4-Acetyl-5-amino-l-(3-chloro( 4,5,6,7-tetrahydropyrazolo[1,5-a]pyridin-2-yl)pyrazole was dissolved in 5 ml dimethoxyethane and treated with 0.28 (0.6 mmol) Lawesson's reagent. After heating under reflux for 2 hours with stirring, the reaction solution was poured into water and extracted with ethyl acetate. The organic phase was washed with saturated aqueous sodium chloride, dried over magnesium sulfate and concentrated.

The residue was purified by silica gel column chromatography. (Hexane/ethyl acetate 1:1).

Yield: 0.21 g = 71% of theory

AP Ο Ο Ο 4 4 Ο

Example 1.2

N-f1-(3-Chloro-4,5,6,7-tetrahydropyrazolof1.5-alpyridin2- vl)-4-nitro-5-pyrazolvl1propionamide

8.72 g (29.7 mmol) N-[1-(3-Chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridin-2-yl)-5-pyrazolyl]propionamide was suspended in 33 ml acetic acid. Under ice cooling, at 0-5°C, 3.31 g (32.5 mmol) acetic anhydride was added.

1.93 g (31 mmol) Fuming nitric acid was added dropwise.

After stirring for 6 hours at room temperature, the mixture was concentrated. The residue was taken up in dichloromethane, neutralised with aqueous sodium hydrogen carbonate and washed with aqueous sodium chloride. The organic phase was dried over magnesium sulfate and concentrated. The residue was purified by silica gel chromatography (hexane/ethyl acetate 1:1).

Yield: 6.03 g = 60% of theory mp: 46-49°C

Example 2.0

Ν-Γ1-(4-Chloro-5-difluoromethoxy-1-methyl-3-pyrazolvl)4-nitro-5-pyrazolyl1-2,2,2-trifluoroacetamide

0.79 g (2.1 mmol) N-[1-(5-Difluoromethoxy-l-methyl3- pyrazolyl)-4-nitro-5-pyrazolyl]-2-2,2-trifluoroacetamide was suspended in 35 ml dichloromethane and treated with 0.17 ml sulfuryl chloride. The mixture was stirred for one hour at room temperature and concentrated.

Yield: 0.77 g = 89.5% of theory mp: 136-139°C

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AP Ο Ο Ο 4 4 Ο

Example 2.1

Ν-Γ1-(4-Chloro-5-difluororaethoxy-l-methyl-3-pyrazolvl) 4-ηitro-5-pyrazolvnacetamide

1.3 g (5.0 mmol) 5-Amino-l-(4-chloro-5-difluoromethoxyl-methyl-3-pyrazolyl)pyrazole was dissolved in 20 ml acetic acid and treated with 0.55 g (5.4 mmol) acetic anhydride. After stirring for 2 hours at room temperature the reaction solution was cooled to 0°C and 0.4 g (6.4 mmol) concentrated nitric acid added. After stirring for 8 hours at room temperature, the reaction mixture was poured into ice water and extracted with ethyl acetate. The organic phase was dried over magnesium sulfate and concentrated. The residue was purified by silica gel column chromatography (hexane/ethyl acetate 1:1).

Yield: 1.4 g = 81.5% of theory mp: 132°C

Example 3.1

5-Amino-4-nitro-l-(4-bromo-5-difluoromethoxy-l-methyl3-pyrazolvl)pyrazole

8.3 g (0.052 mol) Bromine was added dropwise at room temperature to 13 g (0.047 mol) 5-amino-4-nitro25 1-(5-difluoromethoxy-l-methyl-3-pyrazolyl)pyrazole dissolved in 260 ml acetic acid and the mixture stirred for 30 minutes. It was then concentrated and the residue taken up in the ethyl acetate and shaken with 5% aqueous sodium hydrogen carbonate. The phases were separated and the organic phase dried over magnesium sulfate. This was concentrated and the residue purified by silica gel column chromatography (hexane/ethyl acetate 3:1).

Yield: 8.3 g = 49.6% of theory

5 mp: 14 8 °C

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AP Ο Ο Ο 4 4 Ο ο

o

Preparation of the starting materials

1. 5-Amino-4-nitro-l-(5-difluoromethoxy-l-methyl3-pyrazolyl)-pyrazole g (0.065 mol) 5-Amino-l-(5-difluoromethoxy-l-methy13-pyrazolyl)pyrazole was dissolved in 60 ml acetic acid and treated with 7.35 g (0.072 mol) acetic anhydride.

After stirring at room temperature for 3 hours, the reaction mixture was cooled to 10°C. 4.95 g (0.078 mol) Fuming nitric acid was added dropwise and the mixture treated with 8.0 g (0.078 mol) acetic anhydride. After stirring for 18 hours at room temperature, the reaction mixture was added to 500 ml ice-water. It was extracted three times with ethyl acetate, the organic phases were washed with water and concentrated. The residue was treated with 80 ml ethanol and 40 ml concentrated hydrochloric acid. After heating for 8 hours under reflux, the ethanol was removed and the residue extracted with ethyl acetate. The concentrated ethyl acetate phases were washed with saturated aqueous sodium hydrogen carbonate, dried over magnesium sulfate and concentrated. The residue was recrystallised from diisopropyl ether and ethyl acetate .

Yield: 10 g = 56% of theory mp: 140°C

2. 5-Amino-l-(5-difluoromethoxy-l-methvl-3-pyrazolyl)pyrazole

16.5 (0.06 mol) 5-Amino-l-(5-difluoromethoxy-l-methyl3-pyrazolyl)-4-pyrazolecarboxylic acid was heated at 210°C for 5 minutes and then cooled. The congealed melt was recrystallised from diisopropyl ether.

AP 0 Ο Ο 4 4 Ο

Yield: 12.6 g = 92% of theory mp: 106-107°C

3. 5-Amino-l-(5-difluoromethoxy-l-methyl3-pyrazolyl)-4-pyrazolecarboxylic acid

18.9 g (0.06 mol) Ethyl 5-Araino-l-(5-difluoromethoxyl-methyl-3-pyrazolyl)-4-pyrazolyl-4-pyrazolecarboxylate was dissolved in 150 ml 50% ethanol and treated with 15 ml 45% caustic soda. The mixture was heated for 2 hours at 8O°C, the ethanol distilled, the residue treated with icewater and acidified with concentrated hydrochloric acid. The residue was removed by suction filtration, washed with water and dried in vacuo at 75°C.

Yield: 16.7 g = 97% of theory mp: 173°C (dec.)

4. Ethyl 5-Amino-l-(5-difluoromethoxv-l-methyl3-pyrazolvl)-4-pyrazolvl-4-pvrazolecarboxylate g (0.1 mol) 5-Difluoromethoxy-3-hydrazino-l-methylpyrazole was dissolved in 100 ml ethanol. 18.05 g (0.1 mol) Ethyl ethoxymethylenecyanoacetate was added and the mixture heated for 1.5 hours at boiling. After cooling, the precipitated product was removed by suction filtration, washed with some ethanol and dried.

Yield: 18.95 g = 59% of theory mp: 168-169°C

5. 5-Difluoromethoxy-3-hydrazino-l-methyIpyrazole

39.8 g (0.25 mol) 3-Amino-5-difluoromethoxy-l-methylpyrazole was dissolved in 224 ml water and 450 ml concentrated hydrochloric acid. At -10°C, 18.55 g (0.27

BAD ORIGINAL ft

ΑΡοοο44 ο c

c mol) sodium nitrite in 80 ml water was added dropwise. After stirring for 1 hour at -1O°C, 137.6 g tin(II)chloride, dissolved in 180 ml concentrated hydrochloric acid, was added, dropwise, at this temperature. After a further hour stirring at -10°C, 805 ml 32% caustic soda was added dropwise at this temperature. The reaction mixture was shaken 8 times with ethyl acetate, the combined organic phases washed with saturated aqueous sodium chloride, dried over magnesium sulfate and concentrated.

Yield: 42.24 g = 97.2% of theory

Example 3.2

5-Amino-l-(4-bromo-5-difluoromethoxy-l-methy13-pyrazolyl)-4-pyrazolecarbonitrile

5.0 g (20 mmol) 5-Amino-l-(5-difluoromethoxy-l-methyl3-pyrazolyl)-4-pyrazolecarbonitrile was dissolved in 80 ml acetic acid. At room temperature, 1.2 ml (23 mmol) bromine was added, dropwise. After stirring for 15 minutes, the mixture was concentrated and stirred with diisopropyl ether/propanol. The solid material was suction filtered and dried.

Yield: 5.7 g = 87% of theory mp: 160°C

Example 3.3

5-Amino-l-(3-bromo-4,5,6,7-tetrahydropvrazoloΓ1, 5-al-pyridin-2-yl)-4-nitropyrazole

3.6 g (12.7 mmol) 5-Amino-l-(3-bromo-4,5,6,7-tetrahydropyrazolof1,5-a]pyridin-2-yl)pyrazole was suspended in 15 ml acetic acid and treated with 1.23 ml (13.0 mmol) acetic anhydride. The mixture was stirred for 5 hours at room

AP 0 0 0 440 temperature. 1.5 ml (15.9 mmol) acetic anhydride was added and then, with ice-bath cooling, 0.66 ml (15.5 mmol) fuming nitric acid was added, dropwise. After stirring for 12 hours at room temperature, the mixture was concentrated. The residue was dissolved in 30 ml ethanol and treated with 11.2 ml concentrated hydrochloric acid. After heating for 3 hours under reflux, the mixture was concentrated and the residue taken up in water and ethyl acetate. It was made basic with 2N aqueous sodium hydroxide and the organic phase separated. The aqueous phase was extracted twice with ethyl acetate. The combined organic phases were washed once with water and once with saturated aqueous sodium chloride. The organic phase was dried and concentrated. The residue was recrystallised from ethyl acetate.

Example 4.1

1- f3-Chloro-4,5,6,7-tetrahvdropyrazolof1,5-alpyridin2- vl)-5-diethylamino-4-pvrazolecarbonitrile

10.45 g (0.35 mol) Sodium hydride (80%) was added to 100 ml tetrahydrofuran and cooled to O’C. In a nitrogen atmosphere, a suspension of 43.6 g (0.17 mol)

5-amino-l-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridin-2-yl)-4-pyrazolecarbonitrile in 500 ml tetrahydrofuran was added dropwise. The mixture was stirred for 1.5 hours. Then 31.4 ml (0.38 mol) iodoethane in 20 ml tetrahydrofuran was added dropwise at 15°C. After stirring for three hours at 15°C, the mixture was cooled. Water was then added dropwise and the mixture extracted with ethyl acetate. The organic phase was separated, dried and concentrated. The residue was recrystallised from ethyl acetate.

Yield: 47.3 g = 89.4% of theory mp: 68-70 °C

SAD

ORIGINAL

APO 00 4 4 Ο

Example 4.2

1- (3-Chloro-4,5,6,7-tetrahydropyrazolof1, 5-alpyridin2— yl)-5-(ethylmethvlamino)-4-pyrazolecarbonitrile

23.3 g (88.7 mmol) 5-Amino-l-(3-chloro-4,5,6,7-tetrahydropyrazolo[l,5-a]pyridin-2-yl)-4-pyrazolecarbonitrile, 202 ml (1,21 mmol) triethyl orthoformate and 10 drops trifluoroacetic acid was heated for 5 hours with removal of water in a water bath at a temperature of 150°C. The reaction solution was concentrated, the residue was suspended in 250 ml ethanol and treated, portionwise, with cooling with 4.2 g (106.4 mmol) sodium borohydride. The mixture was heated to reflux until no more gas evolution was observed. Then the mixture was concentrated and the residue carefully added to ice-water. The mixture was extracted 3 times with methylene chloride and the extracts dried. The organic phase was concentrated. 2.61 g (87.1 mmol) Sodium hydride (80%) was added to 150 ml tetrahydrofuran and at 0°C, 24.1 g (87.1 mmol) of the resulting 1-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridin-2-yl)-5-methylamino-4-pyrazolecarbonitrile in 500 ml tetrahydrofuran was added dropwise. After stirring for 1 hour at room temperature, 7.82 ml (95.8 mmol) iodoethane was added and the mixture heated at 70°C for 3 hours. Water was added dropwise and the mixture extracted 3 times with ethyl acetate. The organic phase was separated, dried and concentrated. The residue was recrystallised from ethyl acetate.

Yield: 18.97 g = 71% of theory

APOOO 44 Ο

Example 4.3

5-Bromo-1-(4-chloro-5-difluoromethoxy-l-methyl3-pyrazolyl)-4-pyrazolecarbonitrile

5.68 g (19.7 mmol) 5-Amino-l-(4-chloro-5-difluoromethoxyl-methyl-3-pyrazolyl)-4-pyrazolecarbonitrile was dissolved in 66.3 ml hydrobromic acid (47%) and the mixture cooled to -6°C. Under a nitrogen atmosphere, 2.36 g (34.2 mmol) sodium nitrite in 5.9 ml water was added dropwise. The mixture was stirred for 15 minutes at this temperature and heated to room temperature. 200 ml water was then added and the mixture extracted 4 times with methylene chloride. The organic phase was washed with saturated aqueous sodium hydrogen carbonate, dried over magnesium sulfate and concentrated.

Yield: 6.94 g = 99.5% of theory mp: 78 °C

Preparation of the starting materials

1. 5-Amino-1-(4-chloro-5-difluoromethoxv-l-methyl3-pyrazolyl)-4-pyrazolecarbonitrile

5.0 g (19.7 mnol) 5-Amino-l-(5-difluoromethoxy-l-methyl25 3-pyrazolyl)-4-pyrazolecarbonitrile was dissolved in 180 ml acetonitrile and 2.65 g (19.7 mmol) sulfuryl chloride added dropwise. The mixture was stirred for one hour at room temperature and concentrated.

Yield: 5.68 g = 99.5% of theory

AP Ο Ο Ο 4 4 Ο . 5-Amino-1- (5-difluoromethoxy-1-methyl-3-pyrazolvl) 4-pvrazolecarbonitrile

22.5 g (0.13 mol) 5-Difluoromethoxy-3-hydrazino-l-methyl5 pyrazole was dissolved in 310 ml ethanol and treated with

15.4 g (0.13 mol) ethoxymethylenemalononitrile. After the mixture had been heated under reflux for one hour it was cooled. The precipitate was suction filtered and washed with a small amount of ethanol.

ζ-, 10 Yield: 19.28 g = 60% of theory mp: 141-143°C

3. 5-Difluoromethoxy-3-hydrazino-l-methylpvrazole

39.8 g (0.25 mol) 3-Amino-5-difluoromethoxy-l-methylpyrazole was dissolved in 225 ml water and 450 ml concentrated hydrochloric acid. At -10°C, 18.55 g (0.27 mol) sodium nitrite in 80 ml water was added dropwise. After stirring for one hour at -10°C, 137.6 g tin(II)chloride, dissolved in 180 ml concentrated hydrochloric acid, was added dropwise at this temperature. After stirring for a further hour at -10°C, 805 ml 32% t caustic soda was added dropwise at this temperature to the reaction mixture. The mixture was shaken 8 times with ethyl acetate, the combined organic phases washed with aqueous saturated sodium chloride, dried over magnesium sulfate and concentrated.

Yield: 42.24 g = 97.2% of theory

4. 3-Amino-5-difluoromethoxy-1-methylpyrazole

71.7 g (1.79 mol) Sodium hydroxide was added to 600 ml water and the mixture cooled to -5°C. At this temperature, 57.3 g (0.36 mol) bromine was added dropwise at such a rate that the temperature did not rise above 0°C. Then bad original

AP Ο Ο Ο 4 4 Ο

57.1 g (0.3 mol) 3-carbamoyl-5-difluoromethoxy-l-methylpyrazole was added portionwise at 0°C. The reaction mixture was stirred for one hour at 80°C and then saturated with sodium chloride. The precipitate which formed was suction filtered off. The filtrate was shaken 6 times with the ethyl acetate. The organic phase was dried over magnesium sulfate and concentrated. The precipitate which had been removed was dissolved in 500 ml water and the solution heated to boiling point for one hour. The ¢- 10 reaction solution was saturated with sodium chloride and shaken 6 times with ethyl acetate. The organic phase was dried with magnesium sulfate and concentrated.

Yield: 34.2 g = 70.5% of theory 15 mp: 57 °C

5. 3-Carbamoyl-5-difluoromethoxy-l-methylpyrazole

80.6 g (0.39 mol) 3-Methoxycarbonyl-5-difluoromethoxy20 1-methylpyrazole and 300 ml aqueous ammonia (33%) was stirred for one hour under reflux. The reaction solution was cooled, the precipitate suction filtered off and

C washed with water and diisopropyl ether.

Yield: 58.9 g = 78.8% of theory mp: 154°C

6. 5-Difluoromethoxy-3-methoxycarbony1-1-methylpyrazole

67.6 g (0.43 mol) 5-Hydroxy-3-methoxycarbonyl-l-methylpyrazole and 299.2 g (2.17 mol) potassium carbonate was dissolved in 1500 ml dimethylformamide and heated to 70°C. At this temperature chlorodifluoromethane was introduced over 2 hours and the mixture stirred at 80°c for 1.5 hours. The reaction mixture was added to water and bad ORIGINAL

AP 0 0 0 4 4 0 extracted 6 times with ethyl acetate. The combined organic phases were washed with saturated aqueous sodium chloride and dried over magnesium sulfate. The reaction solution was concentrated.

Yield: 80.6 g = 90.3% of theory

7. 5-Hydroxy-3-methoxycarbony1-1-methvlpyrazole

102.3 g (0.72 mol) Dimethyl acetylenedicarboxylate was added to 1000 ml ether and the mixture cooled to -5°C in an ice-methanol bath. 33 g (0.72 mol) methylhydrazine in 100 ml ether was added dropwise at a rate that the inner temperature did not rise above 0°C. The mixture was stirred for one hour at 0°C, the precipitate suction filtered off, washed with ether and dried at 40°C in vacuo. The intermediate was immersed in an oil-bath heated to 120°C. The reaction product was recrystallised from methanol.

Yield: 67.6 g = 60.1% of theory mp: 197 °C

8. 4-Chloro-5-difluoromethoxy-3-methoxycarbony11-methvl-pyrazole

2.1 g (10 mmol) 5-Difluoromethoxy-3-methoxycarbonyl1-methylpyrazole, dissolved in 30 ml methylene chloride, was treated with 1.35 g (10 mmol) sulfuryl chloride and the mixture stirred at room temperature for 10 minutes. It was then concentrated and the residue recrystallised from diisopropyl ether/ethyl acetate.

Yield: 1.8 g = 74.8% of theory mp: 51 °C

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AP Ο Ο Ο 4 4 Ο

Ο

C c

c

Example 4.4

1-(4-Chloro-5-difluoromethoxv-l-methvl-3-pvrazolvl)5-methvl-4-pyrazolecarbonitrile

0.57 g (2.25 mmol) 1-(5-Difluoromethoxy-l-methyl3-pyrazolyl)-5-methyl-4-pyrazolecarbonitrile was dissolved in 30 ml methylene chloride and at room temperature was treated with 0.30 g (2.25 mmol) sulfuryl chloride. The mixture was stirred for one hour and then concentrated.

Yield: 0.65 g = 99.8% of theory mp: 69-70°C

Preparation of the starting materials

1. 1-(5-Difluoromethoxv-l-methvl-3-pvrazolvl)-5-methvl4-pyrazolecarbonitrile

A mixture of 0.79 g (2.91 mmol) 1-(5-difluoromethoxyl-methyl-3-pyrazolyl)-5-methyl-4-pyrazolecarboxamide,

0.46 g (5.85 mmol) pyridine and 20 ml 1,4-dioxane was cooled to 5°C and 0.74 g (3.51 mmol) trifluoroacetic anhydride was added dropwise. The mixture was stirred for 3 hours at room temperature. It was then added to 100 ml water and extracted 4 times with ethyl acetate. The organic phase was dried over magnesium sulfate and concentrated.

Yield: 0.74 = 99.8% of theory mp: 106-107°C

BAD ORIGINAL

AP Ο Ο Ο 4 4 Ο

2. 1-(5-Difluoromethoxv-l-methvl-3-pyrazolyl)-5-methyl4-pyrazolecarboxamide

0.98 g (3.38 mmol) 1-(5-Difluoromethoxy-l-methyl5 3-pyrazolyl)-5-methyl-4-pyrazolecarbonyl chloride was dissolved in 20 ml tetrahydrofuran and 50 ml aqueous ammonia (33%) was added with stirring. After stirring for 3 hours at room temperature, the mixture was concentrated to half and acidified with dilute hydrochloric acid. The precipitate was suction filtered off, washed with a small amount of water and dried.

Yield: 0.27 g = 73% of theory mp: 116-118 °C

3. 1-(5-Difluoromethoxy-1-methyl-3-pyrazolvl)-5-methvl4-pyrazolecarbonyl chloride

0.2 g (3.8 mmol) 1-(5-Difluoromethoxy-l-methyl20 3-pyrazolyl)-5-methyl-4-pyrazolecarboxylic acid was suspended in 30 ml 1,2-dichloroethane and 1.19 g (10.0 mmol) thionyl chloride was added at room temperature, dropwise. The mixture was heated for 1 hour under reflux and concentrated.

Yield: 0.98 g = 100% of theory

4. 1-(5-Difluoromethoxy-l-methyl-3-pyrazolyl)-5-methvl4-pyrazolecarboxylic acid 30

A mixture of 1.25 g (4.16 mmol) Ethyl 1-(5-difluoromethoxy-l-methyl-3-pyrazolyl)-5-methy1-4-pyrazolecarboxylate, 20 ml ethanol and 0.97 ml aqueous sodium hydroxide (45%) was stirred for 1 hour at 80°C. The reaction solution was concentrated to a half and acidified

AP Ο Ο Ο 4 4 Ο with hydrochloric acid (37%). The precipitate was suction filtered off, washed with water and dried.

Yield: 1.05 g = 93% of theory 5 mp: 205-207°C

5. Ethyl 1-(5-difluoromethoxy-l-methyl-3-pyrazolvl)5-methy1-4-pyrazolecarboxylate

3.0 g (16.8 mmol) 5-Difluoromethoxy-3-hydrazino-l-methylpyrazole was added to 25 ml ethanol and treated dropwise with 2.96 g (16.0 mmol) ethyl dimethylaminomethylenacetate dissolved in 25 ml ethanol. The mixture was heated under reflux for 2 hours. After cooling the precipitate was suction filtered off.

Yield: 2.52 g = 53% of theory mp: 100°C

Further starting materials were prepared as follows:

1. 1,1,7-Trichloro-l-hepten-3-one

100 g (0.62 mol) 5-Chlorovaleroyl chloride was added dropwise to 78.53 g (0.589 mmol) aluminium chloride in 150 ml methylene chloride at room temperature. After stirring for 1 hour, 45 ml (0.558 mol) 1,1-dichloroethylene in 25 ml methylene chloride was added dropwise. Under icecooling 100 ml water was added dropwise and solid material suction filtered on Celite.The filtrate was washed with water and the organic phase dried and concentrated. The residue was distilled in a rotary evaporator.

Yield: 112.76 g = 93.8% of theory.

b.p.: 125°C/0.4 mbar bad original

AP Ο Ο Ο 4 4 Ο

2. 2-Hydrazino-4,5,6,7-tetrahydropvrazolof1,5-aTpyridine

261.9 ml (5.4 mol) Hydrazine hydrate was added dropwise to 116.6 g (0.54 mol) 1,1,7-trichloro-l-hepten-3-one in 2000 ml 2-propanol at -2’ C (acetone/dry-ice). After stirring for 12 hours at room temperature 60.6 g (1,08 mmol) potassium hydroxide was added and the mixture heated for 5 hours under reflux. The reaction mixture was evaporated to dryness and the residue treated with 100 ml water and 100 ml brine. It was extracted 9 times with ethyl acetate and the and the organic phase washed with brine, dried over sodium sulfate and concentrated.

Yield: 29.29 g = 35.6% of theory.

Yellow oil

3. 5-Amino-4-cyano-l-(l-methvl-5-methylmercapto3-pyrazolyl)pyrazole

A mixture of 2.0 g (13.1 mmol) 3-Hydrazino-l-methyl5-methylmercaptopyrazole and 1.8 g (14.4 mmol) ethoxymethylenemalononitrile in 25 ml ethanol was stirred for 30 minutes at room temperature and heated at boiling point for 3 hours. The reaction mixture was concentrated and the residue purified by silica gel chromatography (hexane/ethyl acetate 1:1).

Yield 2.8 g = 91% of theory, mp: 165-166° C.

BAD ORIGINAL ft

AP Ο Ο Ο 4 4 Ο

4. 3-Hydrazino-1-methyl-5-methylmercaptopyrazole

1.1 g (15.8 mmol) sodium nitrite in 4 ml water was added dropwise to 1.9 g (13.1 mmol) 3-amino-l-methyl-5-methyl5 mercaptopyrazole in 28 ml concentrated hydrochloric acid at 0° C and the mixture stirred for 2 hours at 0°C. Then, at —30°C, a solution of 7.4 g (32.8 mmol) SnCl₂ . 2H₂O in 5.5 ml concentrated hydrochloric acid was added dropwise and the mixture stirred for 3 hours at this temperature.

The reaction mixture was then made basic with 32% caustic soda and extracted with methylene chloride. The organic phase was dried over sodium sulfate and concentrated. 2.0 g of product was obtained which was used without further purification.

5. 3-Amino-l-methvl-5-methvlmercaptopyrazole

5.55 g (33.0 mmol) 3-amino-4-cyano-l-methyl-5-methylmercaptopyrazole heated with 50 ml 32% caustic soda at boiling for 24 hours. The reaction mixture was cooled, made slightly acidic with aqueous sodium hydrogen phosphate, heated for 8 hours at 50°C and extracted with ethyl acetate. The organic phase was dried over sodium sulfate, concentrated and the residue purified by silica gel chromatography (hexane/ethyl acetate 1:1).

Yield: 19 g = 398% of theory, mp: 164-166° C.

6. 3-Amino-4-cyano-1-methyl-5-methylmercaptopyrazole

9.63 g (56.6 mmol) [Bis(methylmercapto)methylene]malononitrile was suspended in 50 ml water and treated with 3.7 ml (67.9 mmol) methylhydrazine. The mixture was bad ORIGINAL $

AP 0 0 0 4 4 0 heated at boiling for 1 hour, the reaction solution cooled, the precipitate suction filtered and recrystallised from ethanol.

Yield: 6.5 g = 68.% of theory.

mp: 120-121° C.

7. 5-Amino-l-(4,5,6.7-tetrahydropyrazolon,5-alpyridin-2-yl)-4-pyrazolecarboxylic acid and

2-hydrazino-4,5.6,7-tetrahvdro-pyrazolor1,5-alpyridine

These were prepared according to known methods as follows:

a) 2-Amino-4,5,6,7-tetrahydropyrazoloΓ1.5-alpyridine

A solution of 8.19 g (146 mmol) potassium hydroxide in 122 ml water and 122 ml ethanol was added to 19.19 g (292 mmol) hydroxylamine hydrochloride in 200 ml ethanol. The mixture was stirred for 15 minutes, 12.5 g (58 mmol) 2-(2,5-dimethyl-l-pyrrolyl)-4,5,6-7-tetrahydropyrazolo[l,5-a]pyridine added and the mixture heated under reflux for 30 hours. After distilling the ethanol, the mixture was treated with ethyl acetate, solid material filtered off, the aqueous phase saturated with sodium chloride and extracted with ethyl acetate. The organic phase was washed with saturated aqueous sodium chloride, dried over sodium sulfate and concentrated. The crude product was purified by silica gel chromatography (ethyl acetate/methanol).

Yield: 6.12 g = 77% of theory ^lH NMR (CDCl-j, 300MHz): <5=1.75-1.85 (m,2H), 1.95-2,05 (m, 2H) 2.68(t,2H,J=7.5Hz) , 3.5(s(wide),2H) , 3.92(t,2H,J=7.5Hz) , 5.33(s,lH)

BAD ORIGINAL ft

AP000440

b) 2-(2,5-Dimethvl-l-pyrrolvl)-4.5,6,7-tetrahvdropyrazolof1,5-alpyridine g (92 mmol) diethyl azodicarboxylate was added dropwise to 19.7 g (84 mmol) 3(5)-(4-hydroxybutyl)-5(3)(2,5-dimethyl-l-pyrrolyl)pyrazole and 22.1 g (84 mmol) triphenylphosphine in 300 ml tetrahydrofuran under ice cooling. The mixture was stirred for 4 hours at room temperature. It was then concentrated and the residue purified by silica gel chromatography (hexane/ethyl acetate).

Yield: 14.27 g = 79% of theory n£°: 1.5630

c) 3(5)-(4-Hydroxvbutyl)-5(3)-(2,5-dimethyl1-pyrrolyl)pyrazole

A mixture of 18 g (116 mmol) 3(5)-amino-5(3)-(hydroxybutyl) pyrazole, 14.6 g (128 mmol) 2,5-hexanedione and 3.2 ml acetic acid in 100 ml toluene was heated under reflux with removal of water for 8 hours. The resulting precipitate was suction filtered, washed with toluene and dried.

Yield: 19.7 g = 72% of theory mp: 147-148°C

d) 3(5)-Amino-5(3)-(hydroxybutyl)pyrazole

4,8 ml Hydrazine monohydrate was added to a solution of 12.3 g (0.1 mol) tetrahydro-2H-pyran-2-ylidenacetonitrile in 100 ml toluene at room temperature and the mixture

BAD ORIGINAL

AP Ο Ο Ο 4 4 Ο

C ¹⁰ c

c heated under reflux for 5 hours. A dark yellow oil separated. The reaction mixture was concentrated and the residue purified by silica gel chromatography (ethyl acetate/methanol).

Yield: 11 g = 71% of theory

In a similar manner to that described in the previous Examples, the following compounds were prepared.

General formula

AP 0 0 0 4 4 0

Compound Physical

No.	R5	R⁶	mp [°C]
1.3	H	H	80-82
1.4	-CN	H	120-121
1.5	H	-NHCOC₂H₅	149-151
1.6	-CN	-NHCH3	174-175
1.7	-CN	-N(CH₃)₂	138-139
1.8	-CN	•N(C₂H₅)₂
1.9	-CN	-nhcoch₂ci	209-211
1.10	-CN	-N(CH₃)COCH₂C1	109-110
1.11	-CN		131-132
1.12	-no₂	-N(C₂H₅)₂	55-57
1.13	-nc>2	-NHCH3	184-185
1.14	-CN	Cl	176-177
1.15	-CN	Br	196-198
1.16	-no₂	Cl
1.17	-no₂	Br

Constant n_n

1,5432

bad original $

AP Ο Ο Ο 4 4 Ο

Compound

No

R⁵

R⁶

Physical mp[°C]

Constant

1.18

1.19

1.20 1.21 1.22

1.23

1.24

1.25

1.26

1.27

1.28

1.29

1.30

1.31

1.32

1.33

1.34

1.35

1.36

-CN

-NO2

-CN

-NO2

-CN

-NO2

-CN

-CH₃ 168-171

-C₂H₅

-C3H7

-CH₃

-c₂h₅

-C3H7

-OCH3

-OC₂H₅

-OCH3 •OC₂H₅

-OCH(CH₃)CO₂CH₃

-OCH(CH₃)CO2C₂H5

-SCH₃

-SOCH3

-SO₂CH₃

-sc₂h₅

-SCH₂COOEt

-NHCO(CH₂)₂C1 149-150 c

BAD ORIGINAL ft

AP Ο Ο Ο 4 4 Ο

General formula

Compound Physical Constant

No.	Rl	R²	R³	R⁵	, 20 R⁶ mpFC]n_D
2.2	ch₃	-och₃	a	-ΝΟ2	-NHCOCH₃	46-48
2.3	ch₃	-ochf₂	H	H	-nhcocf₃	67-70
2.4	ch₃	-ochf₂	H	H	-N(CH₃)COCH₃	66
2.5	ch₃	-ochf₂	H	-no₂	-nhcoch₃	115-116
2.6	ch₃	-ochf₂	Cl	H	-nhcoch₃	106
2.7	ch₃	-ochf₂	Cl	H	-nhcoc₂h₅	114-119
2.8	ch₃	-ochf₂	Cl	H	-nhcoc₃h₇	80-84
2.9	ch₃	-ochf₂	Cl	H	-nhcoch₂ci	111-115
2.10	ch₃	-ochf₂	Cl	H	-NHCO_<g>	152-156
2.11	ch₃	-ochf₂	Cl	-NO₂	-nhcoc₂h₅	109-110
2.12	ch₃	-ochf₂	Cl	-no₂	-nhcoc₃h₇	92-96
2.13	ch₃	-ochf₂	Cl	-no₂	-nhcoch₂ci	118-120
2.14	ch₃	-ochf₂	Cl	-no₂	^NHCO-^	194-196
2.15	ch₃	-ochf₂	Cl	-no₂	-nhch₃	102-105
2.16	ch₃	-ochf₂	a	-NO2	-N(CH₃)₂
2.17	- (CH	2⁾A-	Cl	-NO2	-nhcoch₃	162 ( dec.)
2.18	- (CH		Cl	-no₂	-nhcoc₃h₇	58-61
2.19	- (CH	z	Cl	-no₂		168( dec)
2.20	ch₃	-ochf₂	Cl	H	-NHCO2C2H5	144-146
2.21	ch₃	-ochf₂	Cl	H	-NHCONH₂

BAD ORIGINAL

AP Ο Ο Ο 4 4 Ο

Compund	R³	Physical Constant
No.	R¹ R²	R⁵ R⁶	20 mp[°C]n_D
2.22	ch₃ -ochf₂	a	H	-nhconhch₃
2.23	ch₃ -ochf₂	a	H	-NHCON(CH₃)₂
2.24	ch₃ -ochf₂	a	-no₂	-NHCO₂C₂H5	1
2.25	ch₃ -ochf₂	a	-no₂	-nhconh₂
2.26	ch₃ -ochf₂	a	-no₂	-nhconhch₃
2.27	ch₃ -ochf₂	a	-NC^	-NHCON(CH₃)₂
2.28	-<^ch2’v	a	-N0₂	-nhco₂c₂h₅
2.29	-<οη₂>₄-	a	-no₂	-nhconh₂
2.30	-<ch₂)₄-	a	-no₂	-nhconhch₃
2.31	-<ch₂)_c	a	-N02	-NHCON(CH₃)₂
2.32	ch₃ -ochf₂	a	-no₂	-och₃
2.33	ch₃ -ochf₂	a	-no₂	-oc₂h₅
2.34	ch₃ -ochf₂	a	-N0₂	-0CH(CH₃)CO₂C₂H₅
2.35	ch₃ -ochf₂	a	-no₂	-sch₃
2.36	ch₃ -ochf₂	a	-N02	-soch₃
2.37	ch₃ -ochf₂	a	-no₂	-SC>2CH₃
2.38		a	-N02	-nhcocf₃	56-60
2.39	ch₃ -ochf₂	a	-no₂	nh6—<(]	44-48
2.40	ch₃ -ochf₂	a	-no₂	o N H JLo _^Q^_q	1.:
2.41	ch₃ -ochf₂	a	-no₂	0 II NHCCHgCClj	47-51
2.42	ch₃ -ochf₂	a	H	ΝΗ0—<ζ]	122-124

BAD ORIGINAL ft

AP Ο Ο Ο 4 4 Ο

General formula

Physical Constant

	Example No.	R³	R⁶	mp [°C]	ⁿD
Ο	2.43	a	CH₂OCH2CO2Me		1.51438
	2.44	a	OLOCHCCLMe I		1.50800
			CH,
	2.45	a	CH.OCCH, II		1.51254
			0
	2.46	Cl	ch₂sch₃		1.54268
c	2.47	a	CH₂SEt		1.53566
c	2.48	a		74
	2.49	a	CH₂SCH₂CO₂Et		1.52740
	2.50	a	CH₂NH₂		1.53932
	2.51	Cl	CH₂NHMe
	2.52	a	CH₂NHEt
	2.53	a	CH₂NH-		1.51362
	2.54	Cl y	CH₂NMe₂
	2.55	Cl	CH₂NEt₂
	2.56	Cl	CH₂N prop₂

AP Ο Ο Ο 4 4 Ο

Example	Physical	Constant
No. R³	R⁶	mp (° C]	ⁿD

2.57	Cl	ch₂och₂ci
2.58	Cl	ch₂och₂cn
2.59	Cl	CH₂ OCH₂-C=CH
2.60	Cl	CH₂O<^HG=CH ch₃
2.61	Cl	CH,O-^0
2.62	Cl	CH₂OCH₂C0₂Et
2.63	Cl	CH₂OCH₂CO₂—
2.64	Cl	CH₂OCH₂CO₂-

BAD ORIGINAL ft

AP Ο Ο Ο 4 4 Ο

Example·	R³	R⁶	Physical Constant
No.			mp [°C] no

4.6	Cl	ch₃	69-70
4.7	Br	ch₃	76-78
4.8	Cl	cf₃	90-93
4.9	Br	cf₃	83- 86
4.10	Cl	C₂H5	74- 76
4.11	Cl	C(CH₃)₃	57- 60
4.12	Cl	ch₂och₃	1.50852 (20 °C)
4.13	Br	ch₂och₃	1.52580
4.14	Cl		118-122
4.15	Cl	ch₂oh	64
4.16	Cl	ch₂ci	54
4.17	Cl	CH₂Br	52
4.18	Cl	CH₂OEt	67
4.19	Cl	CH₂Oprop	48
4.20	a	CH.O—	1.50778 (20 °C)
4.21	Cl	CH₂O(CH₂)₃CH₃	1.50450 (20 ⁹C).

General formula

AP ο Ο Ο 4 4 Ο

Example No.	R¹	R²	R³	R⁶	Physical Constant
mp.: [°C]	ⁿD
4.22	-(CH2)₄-	Br	Br	204-205
4.23	ch₃	ochf₂	a	Br	71-74
4.24	ch₃	ochf₂	Cl	Cl		1.54046
						(20,2 °C)
4.25	ch₃	ochf₂	Br	Br	96- 97

BAD ORIGINAL ft

AP Ο Ο Ο 4 4 Ο

General formula

4.26	Cl	cf₃	109 -	110
4.27	a	c₂h₅	130 -	131
4.28	Cl	c₂f₅	135.5 -	136
4.29	Cl	C3H7	62 -	63
4.30	Cl	CH(CH₃)₂	107 -	108
4.31	Cl	Ph	153 -	154
4.32	Cl	ch₂och₃	84 -	85
4.33	Br	ch₂och₃	80 -	83
4.34	Cl	ch₂oc₂h₅	73 -	74
4.35	Cl	ch₂oc₃h₇	88 -	89
4.36	Cl	CH₂OCH(CH₃)₂		1.5440 (20.1 °C)
4.37	Cl	ch₂oh	106 -	107
4-38	Cl	CH₂Br	128 -	129
4.39	Cl	ch₂och₂och		1.5591 (21.2 °C)
4.40	Cl	ch₂och₂ch=ch₂	100.5 -	102
4.41	Cl	CH₂OCH₂CH₂OCH₃	1.5492 (20,2 °C)
4.42	Cl	ch₂ococh₃	102.5 -	103
4.43	Cl	ch₂och₂cooh	108 -	110
4.44	Cl	ch₂och₂cooch₃		1.5376 (20 °C)

BAD ORIGINAL

APO 00 4 4 Ο

Example No.	R³	R*	Physical Constant
mp: [°C]	ⁿD
4.45	Cl	“'’γΥ.		1.5462(20-1 °C)
4.46	Cl			1.5424 (21 °C)
4.47	Cl			1.5500 (20 °C)
4.48	Cl			1.5481(20,2 °C)
4.49	Cl	CH₂N(C₂H₅)₂		1.5377 (20 °C)
4.50	Cl	ch₂sch₃	100 -101
4.51	Cl	ch₂so₂ch₃	139.5-141
4.52	Cl	ch₂soch₃		1.5716 (20.4 °Q
4.53	Cl	ch₂scooh	120
4.54	Cl	CH2SCH2COOC2H5	1.5641 (20 °C)
4.55	Cl	COOH	184
4.56	Cl	CON(C₂H₅)2	126.5-128

BAD ORIGINAL ft

AP Ο Ο Ο 4 4 Ο

General formula

Example

No.

R³ R⁶

Physical Constant mp: [°C] no

4.57

4.58

4.59

4.60

4.61

4.62

4.63

4.64

4.65

4.66

4.67

4.68

4.69

4.70

4.71

4.72

Cl	NHC3H7	137
Cl	NHCH(CH₃)₂	114
Cl	NH(CH₂-CH=CH₂)	125
Cl	NHC4H9	118
Cl	NH[CH(CH₃)CH₂CH₃]	106
Cl	NH[CH(CH₃)CH(CH₃)₂]	89-92
Cl	nhch₂ch₂och₃	129
Cl	nhch₂ch₂oc₂h₅	111-112
Cl	NHCH(CH₃)CH₂OCH₃	105-106
Cl	NHCH₂CH₂N(CH₃)₂	131-132
Cl	N(CH₃)CH₂CH₂N(CH₃)₂	1 (:
Cl	NHCH₂Ph NHCHj—< 5 0	116
Cl	122-123
Br	N(CH₃)C₂H₅	74- 76
Br	N(CH₃)C₃H₇	93- 95
Cl	N(CH₃)CH(CH₃)₂	74

BAD ORIGINAL ft

AP Ο Ο θ * * Ο

Example No.	R³	R⁶	Physical Constant
mp: [°C]	ⁿD
4.73	Cl	N(CH₃)CH₂-C=CH	91
4.74	Br	N(CH₃)CH₂-ChCH	112-114
4.75	a	N(C₂H₅)CH₂-C=CH₂	75
4.76	a	N(C₂H₅)CH₂-C3CH		1.5642 (21,5
4.77	Cl	N(C₃H₇)₂		1.5468 (23.8 °i
4.78	Cl		156
4.79	Cl		84
4.80	Cl	—N^? \)	107
4.81	a	CN	123
4.82	a	N(C₂H₅)CH₂CH₂N(CH₃)₂		1.5559 (20 °C)
4.83	Cl	N(CH₂-CH=CH₂)₂	79
4.84	Cl	^nhO	145
4.85	a	nhch₂-och	145
4.86	Cl	NHCH(C₂H₅)₂	96
4.87	Cl	^nhO	139-142

BAD ORIGINAL

AP Ο Ο Ο 4 4 Ο

Example No.	R³	R⁶	Physical Constant mp [°C] no
4.88	Cl	-O	141
4.89	Cl	NHCH₂CH2N(C₂H5)2	78-80
4.90	Cl	nhch₂ch₂oh	138
4.91	Cl	NHCH2CH2OCOCH3	99
4.92	Cl	nhch₂ch₂ci	158
4.93	Cl	NH(CH2)3OCH₃	112
4.94	Cl	NHCH2CH2OCH2CH2OH	82-84
4.95	Cl	NHCH₂CH(OCH3)₂	127-129
4.96	Cl	NHCH(CH₃)CH(OCH3)₂	151
4.97	Cl	NHCH₂CH(OC₂H5)2	111-113
4.98	Cl		115-117
4.99	Cl		121-123
4.100	Cl		149-151
4.101	Cl		114.5-117
4.102	Cl	NHCH2CH2SC2H5	113-115
4.103	Cl		170
4.104	Cl		129-131
4.105	Cl	NHCH₂COOC₂H₅	162

BAD ORIGINAL

AP Ο Ο Ο 4 4 0

Example

No.

R³ R⁶

Physical Constant mp [°C] no

4.106

4.107

4.108

4.109

4.110

4.111

4.112 c, a

oV ci

Cl

BAD ORIGINAL ft

General formula

AP O 0 0 4 4 Ο

R3 R⁶

Physical Constant mp: [°C] no

Example

No.

4.113	a	NHC3H7	80
4.114	a	NH-	77
4.115	Cl	NH(CH2)₂OCH3	78-79
4.116	Cl	N(CH₃)C₂H₅		1.52076 (20 °C)
4.117	Cl	N(C₂H₅)₂		1.49924 (20 °C)
4.118	Cl	N(CH₃)CH(CH₃)₂		1.51528 (20 °C)
4.119	Br	N(CH₃)CH(CH₃)₂		1.51258 (20,3 °C)
4.120	Cl	N(C₂H₅)CH(CH₃)₂ 52
4.121	Cl	N(C₃H7)₂		1.49338

(20 °C)

BAD ORIGINAL

AP Ο Ο 0 4 4 0

	72
Example No.	R³ R⁶	Physical Constant mp: [°C] no

V_/

-<

4.122

4.123

Ο

4.124

Br

100 -102

70- 72

1.53388 (21,6 °C)

BAD ORIGINAL A

AP Ο Ο Ο 4 4 Ο

Example R¹ R² R³ R⁶

No.

Physical Constant mp: [°C] no

4.125 -(CH₂)44.126 CH₃ OCHF₂

4.127 CH₃ OCHF₂

4.128 CH₃ OCHF₂

Cl	nhc₂h₅	136
Cl	nhch₃	147-148
Br	nhch₃	150-152
Br	nhc₂h₅	96

4.129	-(CH2)₄-
4.130	-(CH₂)₄-
4.131	-(CH₂)₄-
4.132	-(CH2)4-
4.133	-(CH₂)₄-
4.134	-(CH₂)₄-

Cl NHCH₂CN 183 Cl NHCH₂-C=C-CH₃ 171.5-173.5 Cl nhch₂csc-ch₃Cl NHCH₂-C=C-C₂H₅ci nhch₂-c^c-ch₂-och₃

General formula

APOOOMO

Example

No.

R¹ R² R³ R⁶

Physical Constant mp: [°C] no

4.135

4.136

4.137

4.138

4.139

4.140

4.141

4.142

4.143

4.144

4.145

4.146

4.147

4.148

-(CH2)₄-	Cl	N(CH₃)C₂H₅	69
-(CH2)₄-	Cl	N(CH₃)C₃H₇	89
-(CH2)₄-	Cl	N(CH₃)C₄H₉	72
-(CH2)₄-	Cl	N(CH₃)CH(CH₃)C₂H₅	68
-(CH2)₄-	Cl	N(CH₃)CH(CH₃)CH(CH₃)₂ 70
-(CH2)₄-	Cl	N(CH₃)CH₂CH₂OCH₃	80
-(CH2)₄-	Cl	N(C₂H₅)C₃H₇	92
-(CH2)4-	Cl	N(C₂H₅)C₄H₉	1.5471 (22.9 °C)
-(CH2)₄-	Cl	N(C₂H₅)CH(CH₃)C₂H₅	115
-(CH₂)4-	Cl	N(C₂H₅)CH(CH₃)CH(CH₃)₂	130-133
-(CH₂)₄-	CI	N(C₂H₅)CH₂CH₂OCH₃	58
-(CH2)₄-	Cl	N(C₂H₅)CH₂Ph	110
-(CH₂)₄-	Cl	N(CH₃)CH₂CH₂OC₂H₅	1.5559 (20 °C)
-(CH2)₄-	CI	N(C₂H₅)CH₂CH₂OC₂H₅	1.5484 (20 °C)

BAD ORIGINAL

AP ο Ο Ο 4 4 Ο

Example No.	R¹ R²	R³	R^ Physical Constant
mp: [°C]	ⁿD
4.149	-(CH2)₄-	a	N(C₃H₇)CH₂CH₂OC₂H₅	1.5452 (20 °C)
4.150	-(CH2)₄-	a	N(CH₂-C=CH)CH₂CH₂OC₂H₅ 1.55688 (20 °C)
4.151	-(CH2)4-	a	N(CH₃)CH(CH₃)CH₂OCH₃	1.55644 (20 °C)
4.152	-(CH2)₄-	a	N(C₂H₅)CH(CH₃)CH₂OCH₃	94-95
4.153	-(CH2)₄-	a	N(CH₂-C=CH)CH(CH₃)CH₂OCH₃ 124-126
4.154	ch₃ ochf₂ a	N(C₂H₅)CH₂CH₂OCH₃	1.51744 (19,9 °C)
4.155	ch₃ ochf₂ a	N(CH₂-C=CH)CH₂CH₂OCH₃	1.51376
				(20 °C)
4.156	-(CH2)₄-	a	NH(CH₂-C^CH)	145
4.157	-(CH2)₄-	a	N(CH(CH₃)C₂H₅)CH₂-C=CH	142
4.158	-(CH2)₄-	Cl	N(CH₃)CH₂—	108
4.159	•(CH2)₄-	Cl	N(C₂H₅)CH(CH₃)CH₃	106

BAD ORIGINAL ft

AP Ο Ο Ο 4 4 Ο

Example No.	R¹ R²	R³	R⁶	Physical Constant mp: [°C] n_D
4.160	-(CH2)₄-	Cl	N(C₂H₅)CH(CH₃)₂	106
4.161	-(CH2)₄-	Cl	N(CH₂-C^CH)CH(CH₃)C₂H_{5 142}
4.162	-(CH2)4-	Cl	N(CH₃)CH₂Ph	108
4.163	-(CH2)₄-	Cl	N(CH₃)CH(C₂H₅)₂	110
4.164	-(CH2)₄-	Cl	N(CH3)CH₂CH(OCH₃)₂	71
4.165	-(CH2)₄-	Cl	N(C₂H₅)CH₂CH(OCH₃)₂	1.5459 (20 °C)
4.166	-(CH2)₄-	a	N(CH₂-C=CH)CH₂CH(OCH₃)₂ 111-113
4.167	-(CH2)₄-	Cl	CH,	97-99
4.168	-(CH₂)₄-	CI	A”,	169-171
4.169	-(CH₂)₄-	Cl	CH--OCH	140-142
4.170	-(CH2)₄-	Cl	N(CH₃)CH₂CH₂SC₂H₅	1.5855 (22.4 °C)
4.171	-(CH2)₄-	Cl	N(CH₃)CH₂-C=C-CH₃
4.172	-(CH₂)₄-	Cl	N(CH₃)CH₂-C^c-C₂H₅
4.173	-(CH2)₄-	Cl	N(CH₃)CH₂-CHC-CH₂-OCH₃

BAD ORIGINAL &

AP o 0 0 4 4 0
Example No.	R¹ R²	77
R³	R^ Physical Constant mp: [°C] ηθ
4.174	-(CH2)₄-	Cl	O0
4.175	-(CH2)4·	a	oo
4.176	-(CH2)₄-	a	OL-C3CH OO

BAD ORIGINAL ft

AP Ο Ο Ο 4 4 Ο

V,.

General formula

Example

No.

CN

Physical Constant mp: [°C] no

4.177	Br	N(C₂H₅)₂ 71-72
4.178	Cl	N(CH₂-C=CH)₂	1,5739 1
4.179	Cl	N(CH₂CO₂C₂H₅)₂	1.5427 (20 °C)
4.180	a	108
4.181	Cl	N(CH₂-CSC-CH₃)₂
4.182	Cl	N(CH₂-OC-C₂H₅)₂
4.183	Cl	N(CH₂-C=C-CH₂OCH₃)₂

BAD ORIGINAL ft

APO00 44 0

	79
General formula

Example

No.

CN

R³ R⁶

Physical Constant mp: [°C] nj)

4.184	Cl	NHCOCH3	123
4.185	Cl	NHCOCF3	178
4.186	Cl	NHCOCCI3	224
4.187	Cl	NHCOC2H5	162
4.188	Cl	NHCOC₃H₇	152
4.189	Br	NHCOC₃H₇	148-150
		NHCO—/
4.190	Cl		171
4.191	Cl	NHCOC4H9	103
4.192	Cl	N H CO_	252
4.193	Cl	NHCOCH₂OCH₃	201-203

bad original

AP000440

R³ R⁶

Example

No.

Physical Constant mp: [°C] no

4.194

185-187

4.195

165

4.196

Cl O

151

4.197

Cl vQ

4.198	Cl	o	185
4.199	Cl	NHCON(CH₃)2	168
4.200	a	NHCSN(CH₃)₂	170
4.201	Cl	NHCON(CH₃)Ph	62-64

BAD ORIGINAL

AP o 0 0 4 4 o

General formula

Example No.	R³	R*	Physical Constant
mp: [*C]	°D
4.202		a	weoetywcH, 0	125
4.203		Cl	NHCH₂CO2Et	107-109
4.204		a	NHCXCC^El CH.	111-113
4.205		Cl	N(Et)C0CH3	78-80
4.206		a	N(E0COCH₂C1		1.53412
4.207		a		85-87
4.208		a	N(Et)COEt		1.51132
4.209		a			1.51214
4.210		a	N(^\jcoe X*		1.52582
4.211		a	N(CH₂CO₂Me)COEt	87-90
4.212		Br	NHCOEt	120-122

BAD ORIGINAL ft

APΟ 0 0 4 4 Ο 82

Example No.	R?	R*	Physical Constant mp: [*CJ 00
4.213	Br	NHCOnbutyl	100*104
4.214	Br		103
4.215	Br	N(COEt)2	105-107
4.216	a	NHCOCH3	116-118
4.217	a	NHCOCH^Q	135-137
4.218	a	NHCOCF3	134-137
4.219	a	NHCOC2H5	126-128
4.220	Br	NHCOC3H7	141-144
4.221	a	NHCOC3H7	140-143
4.222	a	NHCO—	96-100
4.223	a	N(COCH3>2	117-119
4.224	a	N(COC₂H₅)2	93- 95
4.225	a	N(COC₃H7)2	73- 76

BAD ORIGINAL

AP € Ο Ο 4 4 Ο

Example No.	R³	R⁶	Physical Constant
mp: [°C]	ⁿD
4.226	Cl	N(CH₃)COCH₃	121
4.227	Cl	N(C₂H₅)COCH₃	79
4.228	Cl	N(C₃H₇)COCH₃	85
4.229	Cl	(CH₂-C=CH)COCH₃	06
4.230	Cl	N(CH₂CH₂OCH₃)COCH₃	128
4.231	Cl	N(CH₂Ph)COCH₃	111-113
4.232	Cl	N(C₂H₅)COCH₂a	98-101
4.233	Cl	N(C₃H₇)COCH₂a	168
4.234	Cl	N(CH₂CH₂OCH₃)COCH₂C1 107
4.235	Cl	N(CH₂CH₂OC₂H₅)COCH₂Cl	1.54132 (20 °C)
4.236	Cl	N(CH₂Ph)COCH₂Cl	165-168
4.237	Cl	N(CH₃)COCF₃	98
4.238	Cl	N(C₂H₅)COCF₃	102
4.239	Cl	N(CH₂-C=CH)COCF₃	137
4.240	Cl	N(CH₃)COC₂H₅	125-128
4.241	Cl	N(C₂H₅)COC₂H₅	83
4.242	Cl	N(CH₂CH₂OC₂H₅)COC₂H₅	1.54132 (20 °C)

BAD ORIGINAL ft

AP ο Ο Ο 4 4 Ο

84
Example No.	R³	R⁶	Physical Constant
mp: [°C]	ⁿD
4.243	Cl	N(CH₃)COC₃H₇	90
4.244	Cl	N(C₂H₅)COC₃H₇	72
4.245	Br	N(C₂H₅)COC₃H₇	103-104
4.246	CI	N (CH _t \|CO_^	121
4.247	Cl	N (c,h,)co_^	122
4.248	Cl	N(CH₍ -CICH)CO_^	191
4.249	σ	n(ch₃)coc₄h₉		1.5427 (23.2 °C
4.250 4.251	a a	N(C₂H₅)COC₄H₉ N(COCH₃)CH₂OCH₃	109	1.5386 (23.3 °C
4.252	a	N[CH(CH₃)₂]COCH₃	112-114
4.253	Cl	N(CH₂CH₂OC₂H₅)COCH₃	100-103
4.254	Cl	N[CH(CH₃)CH(CH₃)₂JCOCH₃ 93
4.255	CI	N[CH(CH₃)₂]COCH₂C1	146-149
4.256	Cl	N[CH(CH₃)C₂H₅]COCH₂C1	109-111
4.257	CI	N[CH(CH₃)CH₂OCH₃]COCH₂C1 126
4.258	, ci	N(CH₂CH₂SC₂H₅)COCH₃		1.5655

(22,4 °C)

BAD ORIGINAL

APO00440

General formula

CN

Example No.	R³	R⁶	Physical Constant
mp: [°C]	ⁿD
4.259	a	N(CH₃)COCH₃	108-109
4.260	Cl	N(CH₃)COCH₂C1	87- 90
4.261	Cl	N(CH₃)COC₂H₅	63- 67
4.262	Cl	N(C₂H₅)COCH₃	77
4.263	Br	N(C₂H₅)COC₃H₇	75- 77
4.264	Cl	N(C₃H₇)COCH₃	78-80
4.265	Br	N(Et)COEt		1.5168
4.266	Br	n (—<jcoet		1.51532
		N<\) COB
4.267	Br			1.53406
4.268	Br	N(CH₂CN)COEt	95-98
4.269	Br	N(Me)COC₃H₇		1.55112
4.270	Br	N(CH₂OCH₃)COC₃H₇	1.53024
4.271	Br	N(CH₂CO₂Et)COC₃H₇	1.52918

BAD ORIGINAL 0)

ΑΡ 0 00 440

General formula

Example No.	R³	R⁶	Physical Constant
mp: [°C]	ⁿD
4.272	a	och₃	174-176
4.273	a	OC₂H₅	117-118
4.274	Br	OC₂H₅	120-122
4.275	CI	OC3H7	95- 96
4.276	Cl	OCH₂CH₂OCH₃		1.55562 (20 °C)
4.277	Cl	och₂ch₂och₂ch₂och₃	1.54220 (20 °C)
4.278	Cl	och₂-c=ch	123
4.279	Cl	OC4H9	74-76
4.280	Cl	%Xj°	99.5-101.5
4.281	Cl		102-104

BAD ORIGINAL

AP ο Ο Ο 4 4 Ο

ρ.

Met

87
Example No.	R³	R⁶	Physical Constant
mp: [°C]	ⁿD
4.282	CI			1.5575 (21.8 °C)
4.283	Cl			1.5520 (22 °C)
4.284	Cl	J?		1.5524 (21.8 °C)
4.285	Cl		67-70
4.286	Cl	OCH₂CH₂CH(OC₂H₅)₂	1.5306 (20 °C)
4.287	Cl		91-93
4.288	Cl			1.5544 (22.7 °C)
4.289	Cl	SCH₂COOCH(CH₃)₂	125
4.290	Cl			1.6136

BAD ORIGINAL ft

AP Ο Ο Ο 4 4 Ο

Example R³

No.

4.291 Cl

4.292 Cl

4.293 Cl

4.294 Cl

4.295 Cl

4.296 a

4.297 Cl

4.298 Cl

4.299 Cl

4.300 Cl

4.301 Cl c

4.302 Cl

4.303 Cl

4.304 Cl

4.305 Cl

4.306 Cl

4.307 Cl

R6 Physical Constant mp: [°C) eg

sch₃	128
sch₂ch₃	62
SCH(CH₃)₂		1.5786 (21.8 °C)
SCH₂-CSCH	94
sch₂co₂c₂h₅		1.5646 (22.5 °C)
SCH(CH₃)CO₂C₂H₅	1.5602 (21.8 °C)
soch₃	163
SO₂CH₃	229
OCH₂CH(CH₃)₂	84-87
OCH₂CH(OC₂H₅)₂		1.5283 (20 °C)
O(CH2)₃OCH₃		1.5482 (20 °C)
OCH₂Ph	120-122
OCH₂CH₂OCH(CH₃)₂ 67-69
	149-152
OCH(CH₃)CO₂C₂H₅
och₂co₂c₂h₅

BAD ORIGINAL

AP 0 0 0 4 4 0

R³ R⁶

Example

No.

Physical Constant mp: [°C] no

4.308

4.309

4.310

4.311

BAD ORIGINAL

AP 0 0 0 4 4 0

General formula

ExampleNo.

R⁶

Physical Constant mp: [°C] n_D

4.312

4.313

4.314

4.315

4.316

4.317

SCH₂CO₂Et 1.53242 (20.2 °C)

SCH₃

SEt

Sprop

S nbutyl

4.318

4.319

4.320

4.321

4.322 och₃

OEt

O prop

BAD ORIGINAL

AP Ο Ο Ο 4 4 Ο

Example

No.

R6 Physical Constant mp: [°C] no

4.323

4.324

4.325

4.326

4.327

4.328

4.329

4.330

4.331

4.332

4.333 nbutyl

A/o.

BAD ORIGINAL &

AP ο Ο Ο 4 4 Ο

	92
Example No.	R<> Physical Constant mp: [°C] no
4.334

4.335

4.336
4.337
4.338
4.339	OB
4.340	O^OO, Me
4.341	•-Ό

4.342	—0
4.343	98-100
4.344	103-105

BAD ORIGINAL Cl

AP 0 0 0 4 4 0

R⁶

Example

No.

Physical Constant mp: [°C] no

4.345

4.346

4.347

4.348

4.349

4.350

4.351

4.352

4.353

4.354 ^hnA o—

HN

93-96

1.51180

101-103

105-108

96-98

BAD ORIGINAL ft

AP 0 0 0 4 4 0

General formula

CHa

Example R⁵ R⁶ Physical Constant

No. mp: [°C] no

4.355	CN	N(C₂H₅)₂	89-90
4.356	CN	^NHfi^CH3 0	123-124
4.357	CN	CH₃
4.358	CN	ch₂och₃
4.359	CN	Br
4.360	CN	Cl
4.361	CN	OCH₂CH₂OCH₃
4.362	no₂	NHCEt II 0

BAD ORIGINAL kA

AP 0 0 Ο 44 Ο

The following examples illustrate the possibilities for use of the compounds of the invention.

In these Examples, herbicidal activity is denoted on a score of 0 to 4 in which:

= no damage

1=1- 24% damage = 25 - 74% damage = 75 - 89% damage = 90 - 100% damage

The abbreviations used for the various plant species have the following meanings

ABUTH = Abutilon theophrasti VERPE = Veronica persica AGRRE = Elymus repens VIOSS = Viola sp

HJWH = Alopecurus myosuroides

AVEFA = Avena fatua

BROTE = Bromus tectorum

CYPDI = Cyperus difformis

CYPES = Cyperus esculentus

ECHGH = Echinochloa crus-galli

GALAP = Galium aparine

GOSHI = Gossypium hirsutum

IPOSS = Ipomea purpurea

MATCH = Matricaria chamomilla

MOOVA = Monochoria vaginalis

ORYSA = Oryza sativa

PANSS = Panicum maximum

PASDS = Paspalum distichum

POLSS = Polygonum sp.

SCPJU = Scirpus juncoides

SEBEX = Sesbania exaltata

SETVI = Setaria viridis

SORHA = Sorghum halepense

SOLSS = Solanum sp.

BAD ORIGINAL

AP ο Ο Ο 4 4 Ο

Te3t Example A

In a greenhouse, the noted plant species were treated pre-emergently with the noted compounds, at a rate of 0.1 kg active ingredient/ha. The compounds were sprayed evenly over the soil as emulsions in 500 litres water/ha. Three weeks after the treatment, the compounds of the invention showed excellent activity against the weeds. The comparison material did not show the same high activity.

BAD ORIGINAL

ΑΡ Ο Ο Ο Μ ο

Compounds	A A	A B	S	F	S	C	A	I	M	P	S	S	V	V
		L G	V R	E	A	o	y	B	P	4	O	E	O	E	I
		0 R	E 0	T	N	R	P	U	o	r	L	B	L	R	0
		M R	F T	V	S	H	#111	T	s		S	E	S	P	s
		y e	A E	'Lr	'S'	A	S' —	R	S	Ks	X	s	E	s
		&			^:W-^:		mill	III		:.«
Ex.	1.1	-	- -	3	3	3	-	3	-	4	2	1	4	3	4
Ex.	1.2	3 -	3 -	4	4	-	-	4	3	4	4	4	4	4	4
Ex.	1.6	3 3	3 -	4	4	3	-	4	-	4	4	3	4	4	4
Ex,	1.7	- -	- -	3	3	3	-	4	-	4	3	4	4	4	2
Ex,	1.8	2 -	- -	2	2	3	-	4	-	4	4	3	4	3	2
Ex.	1.9	2 2	3 -	4	3	3	-	4	-	4	3	3	4	4	4
Ex,	1.11	2 -	3 -	4	3	3	-	3	-	4	1	0	4	4	3
Ex,	1.13	3 -	3 -	4	3	4	2	4	-	4	4	3	4	4	2
Ex.	1.15	3 2	2 -	4	4	2	-	-	-	4	2	2	4	3	4
Ex,	1.18	4 3	3 -	4	4	4	3	4	-	4	4	2	4	4	4
Ex,	2.1	3 4	4 4	4	4	4	3	4	4	4	4	4	4	4	4
Ex.	2.11	3 -	3 -	-	4	4	4	3	4	4	4	4	4	4	4
Ex.	2.12	3 -	3 -	4	4	4	-	4	3	4	4	4	4	4	4
Ex.	2.13	3 -	-	4	4	4	-	3	3	4	4	4	3	4	4
Ex,	2.17	3 3	3 -	4	4	4	-	4	4	4	4	4	4	4	4
Ex.	2.18	3 -	3 -	4	4	3	-	4	-	4	4	2	4	4	4
Ex.	2.24	3 -	3 -	3	3	3	3	4	4	3	4	4	4	4	3
Ex.	2.38	3 -	- -	3	3	-	-	4	3	4	3	4	4	4	4
Ex.	4.12	4 4	4 3	4 4	4	3	4 4	4	4	4	4	4	4	4	4
Untreated	0 0	0 0	0	0	0	0	0	0	0	0	0	0	0	0
Comparison
5-tert-butyl-3-	0 0	0 1	2	4	0	0	1	1	3	1	0	3	2	3
(2,	4-dichloro-5-
isopropoxyphenyl)-
1,3	,4-oxadiazol-	2-one

BAD ORIGINAL

AP Ο Ο Ο 4 4 Ο

Λ -Λ

Test Example Β

In a greenhouse, the noted plant species were treated post-emergently with the noted compounds, at a rate of 0.3 kg active ingredient/ha. The compounds were sprayed evenly over the plants as emulsions in 500 litres water/ha. Two weeks after the treatment, the compounds of the invention showed activity against the weeds. The comparison material did not show the same high activity.

BAD ORIGINAL &

AP Ο Ο Ο 4 4 0 — ₉₉

Compounds	A L O M Y	A G R R E	A V E F A	B R O T E	S E T V I	P A N S S	S Ο R H A	C Y P Sil	A B U T K	G A L A P	F P 0 S S	Μ P A o	S E B E X	S Ο L S S	V E R P E	V Ϊ 0 s s
C H	S S
Ex.	1.0	2	2	2	•	4	3	3		4	3	4	4	4	4	4	4	3
Ex.	1.1	3	3	3	-	4	3	3	-	4	3	3	4	4	4	4	4	3
Ex.	1.2	4	-	3	-	3	-	3	3	4	3	4	4	4	4	4	4	4
Ex.	1.6	4	3	3	2	4	3	3	3	4	3	4	4	4	4	4	4	4
Ex.	1.7	3	3	2	-	3	3	3	-	4	4	4	3	4	4	4	4	4
Ex.	1.8	3	3	3	-	3	3	3	3	4	3	4	3	4	4	4	4	4
Ex,	1.10	-	-	3	-	3	-	3	-	4	-	3	3	4	3	4	4	3
Ex.	1.12	-	-	-	-	3	2	3	-	4	-	3	2	4	3	4	3	3
Ex.	1.13	3	2	3	-	3	3	3	3	4	-	4	4	4	3	4	4	3
Ex.	1.18	3	Ή	3	3	4	3	3	3	4	4	4	4	4	4	4	4	3
Ex.	2.1	3	3	4	4	4	4	3	4	4	4	4	4	4	4	4	4	4
Ex.	2.11	3	3	3	-	4	4	4	-	4	4	4	4	4	4	4	4	4
Ex.	2.12	3	-	4	-	3	3	4	3	4	4	3	4	4	4	4	4	3
Ex.	2.13	3	-	3	-	3	-	3	3	4	3	4	4	4	4	4	4	3
Ex,	2.17	3	3	3	-	4	3	3	3	4	3	4	4	4	4	4	4	3
Ex.	2.18	3	-	3	-	3	3	3	3	4	3	3	4	4	4	4	4	3
Ex.	2.24	3	-	3	-	3	3	3	3	4	3	4	3	4	4	4	4	3
Ex.	2.38	-	3	-	-	3	3	-	-	4	3	3	4	3	4	4	4	4
Ex.	4.12	4	3	4	4	4	4	3	3	4	4	4	4	4	4	4	4	4
Untreated	0	0	0	0	0	0	0	0	0	0	0	0	0	0	0	0	0
Comparison	0	1	1	0	1	0	1	1	4	2	3	2	3	2	4	1	3
5-tert-butyl-3	-
(2,	4-dichloro-	5-
isopropoxyphenyl)	-
1,3	,4-oxadiazol-2	-one

BAD ORIGINAL

AP ο Ο Ο 44 Ο

100

Test Example C

In a greenhouse, the compounds noted in the table were applied at the rates mentioned. For this the formulated active ingredients were pipetted onto the water surface

The test plants were treated pre-emergently and in the 1 3 leaf stage.

BAD ORIGINAL

AP ο ο Ο 4 4 Ο

101

Ex.	1.0	0,04	0	2	4	1	4
Ex.	1.1	0,04	0	3	4	3	4
Ex.	1.17	0,1	0	-	4	-	4
Ex.	1.2	0,005	1	4	4	4	4
Ex.	1.4	0,05	1	3	4	2	4
Ex.	1.5	0,10	0	3	4	1	2
Ex.	1.6	0,04	1	4	4	4	4
Ex.	1.7	0,04	0	4	4	3	2
Ex.	1.8	0,04	0	4	4	4	4
Ex.	1.9	0,0125	0	3	4	J	4
Ex.	1.10	0,01	0	4	4	4	4
Ex.	1.11	0,05	1	4	4	4	4
Ex.	1.13	0,02	1	3	4	2	4
Ex.	1.14	0,02	0	4	4	2	4
Ex.	1.15	0,01	0	1	4	0	4
Ex.	1.18	0,01	2	4	4	3	4
Ex.	1.21	0,025	1	4	4	3	4
Ex.	1.22	0,05	1	4	4	2	4
Ex.	1.29	0,2	0	-	4	3	4
Ex.	1.36	0,04	1	4	4	3	4
Ex.	2.0	0,05	1	3	4	J	4
Ex.	2.1	0,01	1	4	4	4	4
Ex.	2.17	0,01	0	3	-	1	4
Ex.	2.18	0,01	1	3	4	2	4
Ex.	2.38	0,04	0	3	-	2	4
Ex.	3.3	0,08	1	4	4	4	4
Ex.	4.100	0,05	1	4	4	4	4
Ex.	4.101	0,05	1	4	3	3	4
Ex.	4.102	0,025	0	-	4	-	4
Ex.	4.103	0,01	0	-	-	-	4
Ex.	4.104	0,1	1	4	4	3	4
Ex.	4.105	0,05	1	4	4	4	4
Ex.	4.122	0,04	1	-	-	-	4
Ex.	4.125	0,025	0	4	4	4	4
Ex.	4.129	0,1	0	4	4	3	4
Ex.	4.130	0,025	1	4	4	3	4
Ex.	4.135	0,025	1	3	4	3	4
Ex.	4.137	0,1	0	3	-	-	4
Ex.	4.138	0,04	0	-	4	2	3

BAD ORIGINAL ft

AP Ο Ο Ο Μ Ο

102

[COEOpOUJ Wtsfajt&Mai ν/Α/ί'/ά'/ί	' iifpl	MBS βρΒ	gjjail ϋϋ!	Hili sit jgg slgiEj wig		W :θ\|μ '////,::'
Ex.	4.140	0,04		4	4	3	4
Ex.	4.141	0,08	0	3	4	3	4
Ex.	4.143	0,08	0	3	4	3	4
Ex.	4.144	0,04	0	-	4	-	4
Ex.	4.146	0,2	0	4	4	3	4
Ex.	4.147	0,08	0	4	4	2	4
Ex.	4.148	0,08	0	4	4	2	4
Ex.	4.150	0,04	0	4	4	-	4
Ex.	4.151	0,04	0	-	4	-	3
Ex.	4.152	0,1	0	4	3	4	4
Ex.	4.153	0,1	0	4	4	3	4
Ex.	4.154	0,04	0	4	4	2	4
Ex.	4.155	0,04	1	4	4	2	4
Ex.	4.157	0,2	0	4	3	3	4
Ex.	4.158	0,1	0	4	4	4	4
Ex.	4.159	0,1	0	4	4	4	4
Ex.	4.164	0,05	0	4	4	4	4
Ex.	4.165	0,05	0	4	4	4	4
Ex.	4.166	0,05	1	4	4	4	4
Ex.	4.167	0,05	0	4	4	3	4
Ex.	4.168	0,05	0	4	4	3	4
Ex.	4.169	0,05	0	4	4	3	4
Ex.	4.177	0,08	0	4	4	4	4
Ex.	4.178	0,025	0	4	4	4	4
Ex.	4.179	0,1	1	3	4	3	4
Ex.	4.180	0,05	1	4	4	3	4
Ex.	4.185	0,1	1	3	4	2	4
Ex.	4.186	0,1	1	4	-	2	4
Ex.	4.187	0,005	-	3	3	2	3
Ex.	4.189	0,005	1	3	4	3	3
Ex.	4.191	0,02	1	4	4	-	4
Ex.	4.192	0,04	0	-	4	-	3
Ex.	4.194	0,05	1	-	-	3	4
Ex.	4.196	0,1	1	4	3	4	4
Ex.	4.197	0,1	1	4	4	4	4
Ex.	4.198	0,1	0	3	-	-	4
Ex.	4.2	0,025	0	4	-	4	4
Ex.	4.200	0,01	1	3	-	-	4
Ex.	4.205	0,025	1	4	-	4	4

BAD ORIGINAL ft

AP Ο Ο Ο 4 4 ο

103

; Cbsapoyad; , ,'',,; ? ί; ί,ί : ί ί'ί,χι; ί,?; ., , ,6 , Λ//'. ΙίΑ ί.-' ,,i} ',4 ,, ί 1 ,ii '.'; J ί HlJ3 ^:<'·, ‘-Λ'·/'. f$ ~· ' . '; fi Η ; Γ'/ ;' : I 'ffa \ίΑ'ί'·.ίί%ί ii ' ? ' ΐίΑ '''Άΐ} '4/$$%^',	Γ'·^;£&ί?ΜθΗ ίΑηί ί>ί.·^-^Λί;ί>?ί?5ί>ί j'i.'fi.'i'f η.ns,, /, ί-ϊ¹''	-'; mwi Hfi ;c«'? ImiSw A V ·%* , -U'<' ; ίΛΛΛ.ίΑ.ύ:άΑί	νν'ί/άΛΪ'^Ι'ϊ'', i H '
Εχ.	4.206		0,04	0	3	4	2 4
Εχ.	4.228		0,08	0	4	4	3 4
Εχ.	4.230		0,08	1	3	4	2 4
Εχ.	4.234		0,04	0	4	4	3 4
Εχ.	4.26		0,025	0	4	4	3 4
Εχ.	4.27		0,01	1	4	4	2 4
Εχ.	4.227		0,1	1	3	2	3 4
Εχ.	4.229		0,05	1	4	-	4 4
Εχ.	4.231		0,1	0	3	-	4
Εχ.	4.233		0,08	0	4	4	3 4
Εχ.	4.235		0,02	1	3	4	4
Εχ.	4.236		0,2	0	4	4	2 4
Εχ.	4.237		0,04	0	3	4	3 4
Εχ.	4.238		0,04	0	4	4	3 4
Εχ.	4.239		0,04	0	4	4	4 4
Εχ.	4.240		0,08	1	3	4	2 4
Εχ.	4.241		0,04	0	3	4	2 4
Εχ.	4.242		0,04	0	-	4	3
Εχ.	4.243		0,08	0	2	4	2 4
Εχ.	4.244		0,08	0	4	4	3 4
Εχ.	4.245		0,08	0	3	4	2 4
Εχ.	4.246		0,1	0	4	4	4
Εχ.	4.247		0,1	0	4	4	3 4
Εχ.	4.248		0,025	0	3	4	2 4
Εχ.	4.25		0,05	1	4	4	3 4
Εχ.	4.251		0,1	1	3	-	4 4
Εχ.	4.252		0,05	0	-	3	-
Εχ.	4.255		0,1	0	-	-	4
Εχ.	4.257		0,1	0	3	3	4
Εχ.	4.275		0,025	0	4	-	3 4
Εχ.	4.276		0,005	1	4	4	3 4
Εχ.	4.277		0,005	1	-	3	3
Εχ.	4.280		0,1	1	-	3	4
Εχ.	4.281		0,025	1	3	-	2 4
Εχ.	4.288		0,2	0	-	4	4
Εχ.	4.29		0,05	1	4	4	4 4
Εχ.	4.290		0,1	0	3	4	2 4
Εχ.	4.291		0,025	1	4	4	3 4
Εχ.	4.292		0.1	0	4	4	3 4

BAD ORIGINAL

AP Ο Ο Ο Μ Ο

104

Ex.	4.295	0,2	0	3	-	4	4
Ex.	4.31	0,1	0	3	4	3	4
Ex.	4.32	0,005	1	3	4	2	4
Ex.	4.33	0,005	1	-	-	-	4
Ex.	4.34	0,002	1	3	4	2	4
Ex.	4.35	0,005	1	4	4	4	4
Ex.	4.37	0,01	0	3	2	2	4
Ex.	4.38	0,025	1	-	-	-	4
Ex.	4.41	0,005	1	3	4	-	4
Ex.	4.42	0,02	1	4	4	3	4
Ex.	4.43	0,02	1	4	3	2	4
Ex.	4.49	0,25	1	-	3	-	4
Ex.	4.50	0,02	1	3	4	2	4
Ex.	4.56	0,1	1	3	4	2	4
Ex.	4.57	0,025	1	4	-	3	4
Ex.	4.58	0,05	0	4	4	3	4
Ex.	4.59	0,04	0	4	4	4	4
Ex.	4.60	0,1	0	4	4	4	4
Ex.	4.61	0,02	0	4	4	2	4
Ex.	4.62	0,04	0	4	4	2	4
Ex.	4.64	0,04	0	4	4	2	4
Ex.	4.65	0,005	0	3	4	3	4
Ex.	4.66	0,1	0	-	-	-	4
Ex.	4.67	0,1	0	-	-	-	4
Ex.	4.68	0,04	0	4	4	2	4
Ex.	4.69	0,01	0	4	4	2	4
Ex.	4.70	0,08	0	4	4	4	4
Ex.	4.71	0,08	0	3	4	3	4
Ex.	4.73	0,05	0	4	4	4	4
Ex.	4.74	0,08	0	4	4	3	4
Ex.	4.75	0,05	0	4	4	4	4
Ex.	4.76	0,04	0	3	4	2	4
Ex.	4.79	0,04	0	3	-	-	4
Ex.	4.80	0,04	1	4	-	3	4
Ex.	4.82	0,1	0	-	-	-	4
Ex.	4.83	0,1	0	4	4	4	4
Ex.	4.84	0,02	1	3	4	3	4
Ex.	4.85	0,025	0	4	4	3	4
Ex.	4.87	0,1	0	4	4	4	4

AP Ο Ο Ο Μ Ο

105

Compound ; w#?% ι??'-.		M OBI		.¾¾¾¾¾¾¾¾¾ l^wlll ¢^4¾¾¾¾¾¾¾¾¾ 8¾¾¾^¾¾¾¾ il&flBvisil	ιβιι^ fliiS fBWlti IMSm β\|® eMilw	sse WlWil'
Ex.	4.88	0,1	0	4	4	2	4
Ex.	4.89	0,1	0	-	3	-	4
Ex.	4.90	0,025	0	3	-	-	4
Ex.	4.91	0,1	0	4	4	3	4
Ex.	4.92	0,05	1	4	4	4	4
Ex.	4.93	0,025	0	4	4	2	4
Ex.	4.94	0,1	0	-	-	3	4
Ex.	4.95	0,025	1	4	3	3	4
Ex.	4.96	0,005	0	3	4	2	4
Ex.	4.97	0,1	0	4	4	4	4
Ex.	4.98	0,05	1	4	4	3	4
Ex.	4.99	0,025	1	4	4	3	4
Untreated		0	0	0	0	0
As the table shows,	the compounds	of the invention	show
good	activity against Echinochloa	crus	-galli	(ECHGH)
Cyperus difformis (CYPDI), Scirpus juncoides	(SCPJU) and
Monochoria vaginali	s (MOOVA).

AP Ο Ο Ο 4 4 Ο

106

Example D

In a greenhouse, the noted plant species were treated with the noted compounds, at a rate of 0.03 kg active ingredient/ha. The compounds were sprayed evenly over the plants as emulsions in 500 litres water/ha. Two weeks after the treatment, the compounds of the invention showed excellent activity against the weeds. The comparison material did not show the same high activity.

Compound

A

S

P

A

G

I

M

P

S

V

L

E

A

B

A

P

A

0

E

0

E

I

O

T

N

U

L

o

T

L

B

L

R

0

M

V

S

T

A

s

C

S

E

S

P

s

Y

I

s

H

P

s

H

s

X

S

E

s

Ex. 3.1

3

4

3

4

Untreated

0

Comparison

5-tert.-Butyl-3-(2,4-dichloro

1

2

1

3

2

3

2

0

2

4

2

isopropoxyphenyl)-!,3,4-oxadiazol-2-

one

BAD ORIGINAL

AP ο Ο Ο 4 4 Ο

107

Example Ε

In a greenhouse, the noted plant species were treated with the noted compounds, at a rate of 0.1 kg active ingredient/ha. The compounds were sprayed evenly over the plants as emulsions in 500 litres water/ha. Two weeks after the treatment, the compounds of the invention showed excellent activity against the weeds. The comparison material did not show the same high activity.

Compound	A	A	A	B	s	P	S C	A	G	I	Μ P	S S	V	V
	L	G	V	R	E	A	O Y	B	A	P	A O	Ε O	E	I
	O	R	E	0	T	N	R F	U	L	Ο T L	B L	R	o
	M	R	E	T	V	S	Η E	T	A	s	c s	E S	P	s
	Y	E	A	E	I	S	A S	H	P	s	rt s	X s	E	s
Ex. 4.2	-	-	-	-	3	3	3 -	4	3	3	4 4	- 4	4	⁴ !
Ex. 4.3	3	-	3	3	4	4	3 -	4	4	4	4 4	4 4	4	J
Ex. 4.4	4	3	3	3	4	4	3 3	4	4	4	4 4	4 4	4	3 i
Untreated	0	0	0	0	0	0	0 0	0	0	0	0 0	0 0	0	0 :
Comparison
5-tert.-Butyl-3-	1	1	0	0	2	2	1 0	4	2	3	2 3	4 3	2	2
(2,4-dichloro-	5-
isopropoxyphenyl)	-
1,3,4-oxadiazol-2	-one

AP 0 0 0 4 4 0

Claims

Claims

1. Substituted pyrazole derivatives of general formala I (I).

in which

R¹

R² is C-j-C4-alkyl, C-|-C4-alkylthio, C1-C4-alkoxy, each of which is optionally substituted by one or more halogen atoms, or R¹ and R² together form the group -(CH2)_m-;

R³ is hydrogen or halogen;

R⁴ is hydrogen;

R⁵ is hydrogen, nitro, cyano or the group -COOR⁷, -C(=X)NR⁷R⁸ or -C(=X)R¹⁰;

R⁶ is hydrogen, halogen, cyano, C-|-C4-akyl, (optionally substituted by one or more halogen or hydroxy groups), phenyl (optionally substituted by one or more halogen, nitro, cyano, C-|-C4-alkyl, Ci-C4-alkoxy or halo-Ci-C4-alkyl groups), or is a C2-CQalkyl, C3-Cg-alkenyl, Cg-Cg-alkynyl or C3-Cg-alkoxy group, each of which is interrupted by one or more oxygen atoms, or is the group -NR¹¹R¹², r

r.....

-(CH₂)_a-A, -(CH₂)a-O-(CH₂)b-R²². -(CH₂)_a-O-R²³ or-COR²⁴, bad original &

AP 0 0 0 4 4 0

I

-109r, r ' v„ ’

R⁷, R⁸ and R⁹, which may be the same or different, are hydrogen or C-|-C4-aikyl or,

R⁸ and R⁹ together with the nitrogen to which they are attached form a 5 or 6 membered saturated carbocydic ring;

_R10 is hydrogen or C-|-C4-alkyl, optionally substituted by one or more halogen atoms,

R¹¹ is hydrogen, C-|-C4-alkyl, C₂-Cg-alkenyl, C3*Cg-alkynyl or C3-Cg-cycloalkyl, cyanomethyl or the group R²¹CO-;

R12 is C-|-C$-alkyl, C₂-Cg-alkenyl, Cg-Cg-alkynyl or phenyl (each of which is optionally substituted by one or more halogen atoms), C3-CQ-cycloalkyl, cyanomethyl, Ci-C4-alkoxy-C-|-Cg-alkyl, di-C-j-C4-alkylamino-C-j-C4-alkyl, tetrahydrofurfurylmethyl, C3-Cg-alkynyloxy-C-|-C4-alkyl, benzyl oris the group -C(=X)R²¹, 4CH2)a-(O)d-R2⁸, -(CH2)_a-O-(CH₂)_b-R28 or -(CH₂)_a-X-R³⁴, and when R⁵ is -C(=O)R¹⁰, and /or when R¹ is C-|-C4-alkyl, r2 is difluoromethoxy, r3 is bromo and R⁵ is nitro or cyano, R¹² can also be hydrogen; or

R¹¹ and R¹² together with the nitrogen to which they are attached form a 3, 5 or 6 membered saturated carbocydic or aromatic ring, in which a carbon atom is optionally substituted by an oxygen atom;

_r13 is hydrogen, C-j^-alkyl, C₂-Cg-alkenyl or C3-Cg-alkynyl; or

R¹³ and R¹⁴ together form the group -(CH₂)p-;

R^-*⁴ and R^³, which may be the same or different, are C-|-C4-alkyl, C₂-Cg-alkenyl, C3-Cgalkynyl or phenyl (each of which is optionally substituted by one or more halogen atoms), halogen, or the group -XR¹⁸;

_R16 is hydrogen, C-|-Cg-alkyl, C₂-Cg-alkenyl, C3-Cg-alkynyl, C-|-C4-alkylcarbonyl, cyano-C -j -Cg-alkyl, C j -C4-alkoxycarbonyl-C 1 -Cg-alkyl, di-C-)-C4-alkoxycarbonyi-C-|-C4-alkyl, benzyl, C-|-C4-alkoxy-C₂-Cg-alkynyl; or the group -(CH₂)_a-R³³, -(CH2)a-X-R³°, -(CH2)_a-X-(CH₂)_b-R³0 _or-(CH₂)_a-X-<CH₂)_b-X-(CH₂)_c-R³0;

R¹⁷ is hydrogen, Cj-C4-alkyl, C₂-Cg-alkenyl, C3-Cg-alkynyl, cyano-Ci-C3*alkyl, C1-C4alkoxycarbonyi-Ci-C3-alkyl or phenyl, r18 is C-|-C4-alkyl, optionally substituted by one or more halogen atoms;

R21 is C-|-C4-alkyl, (optionally substituted by one or more halogens), C-|-C4-alkoxyC<|-C4-alkyl, C-|-C4-alkylthio-C-|-C4-alkyl, C3-Cg-cycloalkyl or is the group -NR³¹R³² or 4CH₂)_a-(O)_d-R³³;

R22 is C-]-C4-alkoxycarbonyl or carboxy;

r23 is chloromethyl, cyanomethyl, C3-Cg-cycloalkyl, (optionally interrupted by one or more oxygen atoms);

r24 is hydroxy or the group -NR²³r26;

A is-NR25R26_or._S(_O)_nR27_; r25 _and r26 _Which may be the same or different, are hydrogen or C-|-C4-alkyl;

R²⁷ is C<|-C4-alkyl, C1 -C4-alkoxycarbonyl-C-| -C4-alkyl or carboxy;

BAD ORIGINAL

AP 0 0 0 4 4 0

-11Or28 is hydrogen, hydroxy, halogen, C-]-C4-alkyl, (optionally substituted by one or more

C-|-C4-alkoxy groups), C3-Cg-cycloalkyl (optionally interrupted by one or more oxygen atoms and optionally substituted by dimethyl), furyl, thienyl or -C(=O)R²⁹;

R29_and R³⁰, which may be the same or different, are C-|-C4-alkyl or C-|-C4-alkoxy;

R³¹ and R³², which may be the same or different, are C-|-C4-alkyl or phenyl;

R³³ is C3-C(5-cycloalkyl (optionally interrupted by one or more oxygen atoms and optionally substituted by dimethyl) or -C(=O)R²⁹;

R³⁴ is C-)-C₄-alkyl; a, b and c are 1, 2 or 3; d is 0 or 1;

m is 3 or 4;

n is 0, 1 or 2;

p is 2 Oder 3; and

X is oxygen or sulfur.t

BAD ORIGINAL

V'·

IllAP Ο Ο Ο 4 4 Ο
2. Substituted pyrazolyl derivatives according to claim 1 in which

R¹ is methyl;

R² is methylthio or difluoromethoxy (and especially 5 difluoromethoxy); or

R¹ and R² together form the group -(CH₂)₄;

R³ is hydrogen, chloro or bromo;

R⁴ is hydrogen;

R⁵ is hydrogen, nitro, cyano or -C(=X)R¹⁰.
3. Substituted pyrazolyl derivatives according to claim 1 or 2 in which R⁶ is hydrogen, halogen, cyano, Cj-C₄-alkyl, Cj^-alkylthio or -NRⁿR¹²,

15
4. Substituted pyrazolyl derivatives according to claim 3 in which R¹¹ and R¹², which may be the same or different are hydrogen, Cj^-alkyl or C^-alkoxycarbonyl.
5. Compounds of general formula Ila ( 2

3 0 in which R¹, R² and R³ have the meanings given in general formula I in claim 1, as intermediates for preparation of compounds claimed in claim 1.

BAD ORIGINAL ft

AP Ο Ο Ο 4 4 Ο

-112(Ί> €
6. Compounds of general formula Ii (Ii), in which R¹ and R² have the meanings given in general formula I in claim 1, as intermediates for preparation of compounds claimed in claim 1.
7. Compounds of general formula Ij

N— in which R¹, R² and R⁵ have the meanings given in general formula I in claim 1, as intermediates for preparation of compounds claimed in claim 1.

bad ORIGINAL

AP Ο Ο Ο 4 4 Ο

-1138. Compounds cf general formula Ik in which R¹, R² and R⁶ have the meanings given in general formula I in claim l, as intermediates for preparation of compounds claimed in claim 1.
9. Compounds of general formula II

N —

R (II) , in which R¹, R² and R³ have the meanings given in general formula I in claim l, as intermediates for preparation of compounds claimed in claim 1.

BAD ORIGINAL ft

AP Ο Ο Ο 4 4 Ο (ΐ'

-11410. Compounds of general formula Im ( Im ) in which R¹, R², R³ and R⁶ have the meanings given in general formula I in claim 1, as intermediates for preparation of compounds claimed in claim 1.

11. A herbicidal composition which comprises a compound according to any one of claim 1 to 4, in admixture with agriculturally acceptable carriers and diluents.

20 12. A method of combating weeds which comprises applying to the weeds or their locus a compound according to any one of claims 1 to 4.

13. A process for the preparation of a compound of general 25 formula I as claimed in claim 1, in which

A) a compound of general formula II

F.

(II), nhnh₂ in which R¹, R² and R³ have the meanings given in formula I, is reacted with a compound of general general formula

III

BAD ORIGINAL

AP Ο Ο Ο 4 4 Ο

-115/ \

Υ CN (ΝΙ), in which R⁴ and R⁵ have the meanings given in general formula I and Y is Cj-Cg-alkoxy, hydroxy or halogen, or when R⁵ is hydrogen,
10 B) a compound of general formula II •N

N^: /

/ /

\ (II)

NHNHin which R^l, R² and R³ have the meanings given in general formula I, is reacted with a 2-haloacrylonitrile of

20 formula Ilia

-CN

-r'' »2(Ilia),

Hai or with a 2,3-dihalopropionitrile of formula IHb

Hai^H₂ — CH

CN (I I I b )_;

HaJ in which Hal is halogen, or when R³ is halogen,

35 C) a compound of general formula la

BAD ORIGINAL ft

ί.. j

V

AP 0 Ο Ο 4 4 Ο

116

Ν

R

Pa), in which R¹, R², general formula agent to give a

He!

\_ ⁵, R¹¹ and R¹² have

I, is reacted first compound of formula N— > I /N !

the meanings given in with a halogenating lb (lb), in which R¹, R², R⁵, R¹¹ and R¹² have the meanings given in general formula I, and Hal is halogen, and then further treated to give the desired compound, or when R⁵ is -C(=S)R¹⁰ and R⁶ is amino,

D) a compound of general formula Ic (Ic) .

O in which R¹, R², R³, R⁴ and R¹⁰ have the meanings given in general formula I, is Created with Lawesson's reagent, that is 2,4-bis(4-methoxyphenyl)-I,2,3,4-dithiadiphosphetan—2,4-dithion, or when R³ is -OR

BAD ORIGINAL ft

AP Ο Ο Ο 4 4 Ο

-117Ε) a compound of general formula Id in which R¹, R², R³, R⁴ and R⁵ have the meanings given in general formula I, is first diazotised to give a compound of formula le

R⁴

R ' (I e) in which R¹, R², general formula of formula If

R³, R⁴ and R⁵ have the meanings given in I, and then by heating to give a compound in which R¹, R², R³, R⁴ and R⁵ have the meanings given in general formula I, which is then reacted with a compound of general formula IV

QR¹⁶ (IV) in which R¹⁶ has the meaning given in general formula I, and Q is a leaving group, or when R⁵ is nitro and R⁶ is -SR¹⁷,

BAD ORIGINAL Ά

AP Ο Ο Ο 4 4 Ο

-118F) a compound of general formula Ig R² c 1 I

N~^Z

V^Ny-^{R 4}

Hal (ig)

NO,

10 in which R¹, R², R³ and R⁴ have the meanings given in general formula I and Hal is halogen is reacted with a nucleophile of general formula V ^eSR¹⁷ (V) m which R¹' has the meaning given in general formula I, or
15 when R⁵ is nitro and R⁶ is -S(O) R¹⁷, in which n is l or 2,

G) a compound of general formula Ih (lh), in which R¹, R², R³, R⁴ and R¹⁷ have the meanings given in general formula I, is subjected to a stepwise oxidation with £i-chloroperbenzoic acid, or when R^s is cyano

H) a compound of general formula Ila

R (Ha);

N^: nhnh₂ in which R^l and R² have the meanings given in general

BAD ORIGINAL

AP Ο Ο Ο 4 4 Ο

-119formula I, is reacted with a compound of general formula IIIc CN /~=\ (Me),

Y CN in which Y is Cj-Cg-alkoxy, hydroxy or halogen, or when R⁵ is nitro,

I) a compound of .general formula Ii

R in which R¹ and R² have the meanings given in general formula I, is nitrated in known manner, or

J) a compound of general formula Ij in which R¹, R² and R⁵ have the meanings given in general formula I, is brominated in known manner, or when when R⁵ is halogen,

K) a compound of general formula II

NHNH, (II) ,

BAD ORIGINAL

AP 0 0 0 4 4 0

-120CN ’ \

CN in which R^l, R² and R³ have the meanings given in general formula I, is reacted with a compound of general formula IIIc (me),

Y in which Y' is C^-c₆-alkoxy, dimethylamino or halogen, to first give compound of formula II

II) in which R^l, R² and R³ have the meanings given in general formula I, and this compound is then diazotised in known
20 manner with sodium nitrite and converted to the corresponding halide, or L) a compound of general formula Ik (^Ik), in which R¹, R² and R⁶ have the meanings given in general formula I, is treated with a halogenating agent, or

BAD ORIGINAL ft

AP Ο Ο Ο 4 4 Ο

-121Μ) a compound of general formula Im

N— (^Im;,

Π ¹ in which R^l, R² and R³ have the meanings given in general formula I, and R⁶ is Cj-C^-alkyl, (optionally substituted by one or more halogens) or is a C^-Cg-alkyl, interrupted by one or more oxygens, is converted in known manner to the nitrile of general formula I, or when R⁶ is -NR^UR¹², N) a compound of general formula In (In ) ,

CN in which R¹, R² and R³ have the meanings given in general formula I, is reacted with an amine in a solvent, or when

R⁶ is

-NR^R¹², in which R¹¹ is hydrogen and R¹· is ,11

Cj-Cg-alkyl,

0) a compound of general formula II

N— (II) , in which R¹, R² and R³ have the meanings given in general formula I, is reacted with a trialkyl ortho ester and then reduced, or bad original 8

AP Ο Ο Ο 4 4 Ο

-122Ρ) a compound of general formula Io (io ) in which R¹, R² and R³ have the meanings given in general 10 formula I, and R¹² is Cj-C₆-alkyl is reacted with an base and an alkylating agent or an acid chloride, or when R⁶ is -NRⁿR¹², in which R¹¹ and R¹² are CpC^-alkyl,

Q) a compound of general formula 11 in which R¹, R² and R³ have the meanings given in general formula I, is reacted with approximately 2 mole of base and 2 mole of a suitable alkylating agent, or

R) a compound of general formula II

N/ in which R¹, R² and R³ have the meanings given in general formula I, is reacted with or without a base and a suitable acid chloride, or

BAD ORIGINAL ft

AP Ο Ο Ο 4 4 Ο

-123S) a compound of general formula Ip N— : /

R

CN

NH

C = 0 ¹ 01 a² in which R¹, R², R³ and R²¹ have the meanings given in general formula I, is reacted with a base and a suitable alkylating agent, or

T) a compound of general formula In

N— in which R¹, R² and R³ have the meanings given in general formula I and R⁵ is cyano or nitro, is reacted with an oxygen, nitrogen, sulfur or carbon nucleophile, or when R⁶ is substituted methyl

U) a compound of general formula Iq

Λ in which R^l, R², R³, R⁴ and R⁵ have the meanings given in general formula I, is reacted with a Lewis acid, or bad ORIGINAL

AP Ο Ο Ο 4 4 Ο

-124V) a compound .of general formula Ir \V //'

-R r·

CH,

OK (I Ό, in which R¹, R², R³, R⁴ and R⁵ have the meanings given in general formula I, is treated with a halogenating agent, or

W) a compound of general formula Is 4

R in which R¹, R², R³, R⁴ and R⁵ have the meanings given in general formula I, is reacted with an oxygen, nitrogen, sulfur or carbon nucleophile, or when R⁶ is mercapto X) a compound of general formula It

R (- t)

I i •«s

Λ in which R^l, R², R³ and R⁴ have the meanings given in

BAD ORIG'NAL Q

AP Ο Ο Ο 4 4 Ο —125— general formula I, is treated with sodium hydrogen sulfide, or

Y) a compound of general formula Iu 4

Λ in which R¹, R², R³ and R⁴ have the meanings given in general formula I, is treated with a suitable alkylating agent, or

Z) a compound of general formula Iv in which R¹, R², R³ and R⁴ have the meanings given in general formula I, and R^x is Cj-C₄-alkyl, is oxidised in stages.