WO2004002981A2 - Herbicidal thienylalkynes - Google Patents

Abstract

Compounds of formula (I), wherein the substituents R1, R2, R3 and R4 and the suffixes n and m are as defined in claim 1, and also the agrochemically acceptable salts and all stereoisomers and tautomers of such compounds, are suitable for use as herbicides.

Description

Novel herbicides

The present invention relates to novel, herbicidally active thienylalkynes, to processes for their preparation, to compositions comprising such compounds, and to their use in the control of weeds, especially in crops of useful plants, or in the inhibition of plant growth.

Phenylalkynes having herbicidal action are described, for example, in JP-A-11 147 866, WO 01/55066 and WO 02/28182, and pyridylalkynes are descπbed, for example, in WO 03/013247, PCT Application No. EP02/14006 and CH Application No. 558/02.

Novel thienylalkynes having herbicidal and growth-inhibiting properties have now been found.

The present invention accordingly relates to compounds of formula I

wherein n is 0, 1 , 2, 3, 4 or 5; each R_! is independently halogen, -CN, -SCN, -SF₅, -NO₂, -NR₅R₆, -CO₂R₇, -CONR₈R₉₎

-C(Rιo)=NORn, -COR₁₂, -OR_13> -SR₁₄, -SOR₁₅, -SO₂R₁₆, -OSO₂R₁₇, C C₈alkyl, C₂-C₈alkenyl,

C₂-C₈alkynyl or C₃-C₆cycloalkyl; or Cι-C₈alkyl, C₂-C₈alkenyl or C₂-C₈alkynyl substituted from one to five times by halogen and/or once, twice or three times by -CN, -NO₂, -NR₁₈R₁₉, -

CO₂R₂o, -CONR21R22, -COR₂₃, -C(R₂₄)=NOR₂5, -C(S)NR₂₆R₂₇, -C(C C₄alkyltrιio)=NR₂₈, -

OR₂₉, -SR30, -SOR₃₁, -SO₂R32 or C₃-C₆cycloalkyl; and/or each R-i is C₃-C₆cycloalkyl substituted from one to five times by halogen and/or once, twice or three times by -CN, -NO₂, -NR₁₈R₁₉, -CO₂R₂o, -CONR₂₁R₂₂, -COR₂₃, -C(R₂₄)=NOR₂₅,

-C(S)NR₂₆R₂₇, -C(C₁-C₄alkylthio)=NR₂₈, -SR₃₀, -SOR_{31 l} -SO₂R₃₂ or C₃-C₆cycloalkyl; and/or each Ri is independently phenyl, which may itself be substituted from one to five times by halogen and/or once, twice or three times by d-C^lkyl, CrC₄haloa!kyl, C C alkoxy, -CN,

-NO₂, C-|-C₄alkylthio, C-ι-C₄alkylsulfinyl or CrC₄alkylsulfonyl; and/or two adjacent R^ together form a Cι-C₇alkylene bridge, which may be interrupted by 1 or 2 non-adjacent oxygen atoms and substituted by C C₆alkyl, the total number of ring atoms being at least 5 and at most 9; and/or two adjacent R₁ together form a C₂-C₇alkenylene bridge, which may be interrupted by 1 or 2 non-adjacent oxygen atoms and substituted by d-Cβalkyl, the total number of ring atoms being at least 5 and at most 9;

R₃ and R₄ are each independently of the other hydrogen, halogen, -CN, d-C₄alkyl or C C₄- alkoxy; or

R₃ and R₄ together are C₂-C₅alkylene;

R₅ is hydrogen or d-C₈alkyl;

R₆ is hydrogen, C_rC₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by C C₄alkyl, Cι-C₄haloalkyl, C C₄alkoxy, -CN, -NO₂, d-C alkylthio,

CrC₄alkylsulfinyl or d-C₄alkylsulfonyl; or

R₅ and R₆ together are a C₂-C₅alkylene chain, which may be interrupted by an oxygen atom or a sulfur atom;

R₇ is hydrogen, d-C₈alkyl, C₃-C₈alkenyl or C₃-C₈alkynyl, or Cι-C₈alkyl, C₃-C₈alkenyl or

C₃-C₈alkynyl substituted from one to five times by halogen or once, twice or three times by

C C alkoxy or phenyl, wherein phenyl may itself be substituted from one to five times by halogen and/or once, twice or three times by C C₄alkyl, C₁-C₄haloalkyl, Cι-C alkoxy, -CN,

-NO₂, Cι-C alkylthio, C C alkylsulfinyl or Cι-C₄alkylsulfonyl;

R₈ is hydrogen or C Csalkyl;

R₉ is hydrogen or CrC₈alkyl, or Cι-C₈alkyl substituted once, twice or three times by COOH,

Gι-C₈alkoxycarbonyl or -CN; or

R₉ is C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by C C₄alkyl, C C₄haloalkyl, C_rC₄alkoxy, -CN, -NO_2l d-C₄alkylthio, C C₄alkylsulfinyl or Cι-C₄alkylsulfonyl; or

R₈ and R₉ together are C₂-C₅alkylene;

R₁₀ is hydrogen, Cι-C₄alkyl, Cι-C₄haloalkyl or C₃-C₆cycloalkyl;

Ru is hydrogen, d-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, C C₄haloalkyl or C₃-C₆haloalkenyl;

R₁₂ is hydrogen, d-C₄alkyl, Cι-C₄haloalkyl or C₃-C₆cycloalkyl;

R₁₃ is hydrogen, Cι~C₈a!kyl, C₃-C₈alkenyl or C₃-C₈alkynyl; or

R₁₃ is phenyl or phenyl-d-C₆alkyl, wherein the phenyl rings may themselves be substituted from one to five times by halogen and/or once, twice or three times by Cι-C₄alkyl, Cι-C₄halo- alkyl, d-C₄alkoxy, -CN, -NO₂ or -S(O)₂d-C₈alkyl; or R₁₃ is d-C₈alkyl substituted from one to five times by halogen or once, twice or three times by -CN or C C₄alkoxy;

R_i4 is hydrogen, C C₈alkyl, C₃-C₈alkenyl or C₃-C₈alkynyi, or C C₈alkyl substituted from one to five times by halogen or once, twice or three times by -CN or C C alkoxy;

R₁₅, R₁₆ and Rι₇ are each independently of the others C C₈alkyl, C₃-C₈alkenyl or C₃-C₈- alkynyl, or C C₈alkyl substituted from one to five times by halogen or once, twice or three times by -CN or d-C alkoxy;

R₁₈ is hydrogen or d-C₈alkyl;

R₁₉ is hydrogen, CrC₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by C_rC₄alkyl, d-C₄haloalkyl, C C₄alkoxy, -CN, -NO₂, d-C₄alkylthio, d-C₄- alkylsulfinyl or d-C₄alkylsulfonyl; or

R₁₈ and R₁₉ together are a C₂-C₅alkylene chain, which may be interrupted by an oxygen atom or a sulfur atom;

R₂₀ is hydrogen, C C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by C C₄alkyl, d-C₄haloalkyl, d-C₄alkoxy, -CN, -NO₂, Cι-C₄alkylthio, d-C alkylsulfinyl or C C₄alkylsulfonyl;

R₂₁ is hydrogen or Cι-C₈alkyl;

R₂₂ is hydrogen or d-C₈alkyl, or Cι-C₈alkyl substituted once, twice or three times by COOH, d-C₈alkoxycarbonyl or -CN, or

R₂₂ is C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by d-C₄alkyl, C C₄haloalkyl, C C₄alkoxy, -CN, -NO₂, C C₄alkylthio, C C₄alkylsulfinyl or d-C₄alkylsulfonyl; or

R₂₁ and R₂₂ together are C₂-C₅alkylene;

R₂₃ is hydrogen, C C₄alkyl, C C₄haloalkyl or C₃-C₆cycloalkyl;

R₂ is hydrogen, C_rC alkyl, C C₄haloalkyl or C₃-C₆cycloalkyl;

R₂₅ is hydrogen, C C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, C C haloalkyl or C₃-C₆haloalkenyl;

R₂₆ is hydrogen or d-C₈alkyl;

R₂₇ is hydrogen or Cι-C₈alkyl, or d-C₈alkyl substituted once, twice or three times by COOH,

C C₈alkoxycarbonyl or -CN; or

R₂₇ is C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by C C₄alkyl, d-C₄haloalkyl, C C₄alkoxy, -CN, -NO₂₎ d-C₄alkylthio, Cι-C₄alkylsulfinyl or C C₄alkylsulfonyl; or R₂₆ and R₂₇ together are C₂-C₅alkylene;

R₂₈ is hydrogen or d-C₈alkyl;

R₂₉ and R₃₀ are each independently of the other hydrogen, d-C₈alkyl, C₃-C₈alkenyl or C₃-C₈- alkynyl, or C C₈alkyl substituted from one to five times by halogen or once, twice or three times by -CN or d-C₄alkoxy;

R₃₁ and R₃₂ are each independently of the other Cι-C₈alkyl, C₃-C₈alkenyl or C₃-C₈alkynyl, or d-C₈alkyl substituted from one to five times by halogen or once, twice or three times by -CN or d-C alkoxy; m is 0, 1 , 2 or 3; each R₂ is independently halogen, -CN, -SCN, -SF₅₎ -NO₂₎ -NR₃₆R₃₇, -CO₂R₃₈, -CONR₃₉R_40>

-C(R₄₁)=NOR₄₂, -COR₄₃, -OR^, -SR₄₅, -SOR₄₆₎ -SO₂R₄₇, -OSO₂R₄₈, -N([CO]_pR₄9)COR₅o,

-N(OR₅ι)COR₅₂, -N(R₅₃)CO₂R₅₄ or -N-phthalimide;

R₃₆ is hydrogen or Cι-C₈alkyl; and

R₃₇ is hydrogen, d-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by C C₄alkyl, C C₄haloalkyl, d-C₄alkoxy, -CN, -NO₂, C C₄alkylthio, C C₄- alkylsulfinyl or Cι-C alkylsulfonyl; or

R₃₆ and R₃₇ together are a C₂-C₃alkylene chain, which may be interrupted by an oxygen atom or a sulfur atom;

R₃₈ is hydrogen, C C₈alkyl, C₃-C₈alkenyl or C₃-C₈alkynyl, or d-C₈alkyl, C₃-C₈alkenyl or

C₃-C₈alkynyl substituted from one to five times by halogen or once, twice or three times by

CrC₄alkoxy or phenyl, wherein phenyl may itself be substituted from one to five times by halogen and/or once, twice or three times by Cι-C₄alkyl, d-C₄haloalkyl, d-C₄alkoxy, -CN,

-NO₂, C C alkylthio, d-C₄alkylsulfinyl or C C₄alkylsulfonyl;

R₃₉ is hydrogen or Cι-C₈alkyl;

R₄₀ is hydrogen or d-C₈alkyl, or C C₈alkyl substituted once, twice or three times by -COOH, d-C₈alkoxycarbonyl or -CN; or

R₄₀ is C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by C C₄alkyl, C C₄haloalkyl, C C₄alkoxy, -CN, -NO₂, d-C₄alkylthio, C C₄alkylsulfinyl or Cι-C₄alkylsulfonyl; or

R₃₉ and R₄₀ together are C₃-C₅alkylene;

R₄₁ is hydrogen, C C₄alkyl, C_rC₄haloalkyl or C₃-C₆cycloalkyl;

R₄₂ is hydrogen, d-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, C C₄haloalkyl or C₃-C₆haloalkenyl;

R^ is hydrogen, C C₄alkyl, C C₄haloalkyl or C₃-C₆cycloalkyl;

R^ is hydrogen, C C₈alkyl, C₃-C₈alkenyl or C₃-C₈alkynyl; or R^ is phenyl or phenyl-d-C₆alkyl, wherein the phenyl rings may themselves be substituted from one to five times by halogen and/or once, twice or three times by d-C alkyl, d-C₄halo- alkyl, C C₄alkoxy, -CN, -NO₂ or -S(O)₂C C₈alkyl, or

R^ is d-C₈alkyl substituted from one to five times by halogen or once, twice or three times by -CN or C C alkoxy;

R₄₅ is hydrogen, d-C₈alkyl, C₃-C₈alkenyl or C₃-C₈alkynyl, or C C₈alkyl substituted from one to five times by halogen or once, twice or three times by -CN or C C₄alkoxy;

R ₆, R₄₇ and R₄₈ are each independently of the others d-C₈alkyl, C₃-C₈alkenyl or C₃-C₈- alkynyl, or Cι-C₈alkyl substituted from one to five times by halogen or once, twice or three times by -CN or d-C₄alkoxy; p is 0 or 1 ;

R ₉, Rδo_> R5₁, R5₂, R53 and R₅₄ are each independently of the others hydrogen, CrC₈alkyl or phenyl, which may itself be substituted from one to five times by halogen and/or once, twice or three times by d-C₈alkyl, C C₄haloalkyl, C C₄alkoxy, -CN, -NO₂, d-C₈alkylthio, d-C₈- alkylsulfinyl or d-C₈alkylsulfonyl; and/or each R₂ is independently CrC₈alkyl, or d-C₈alkyl substituted from one to five times by halogen or once, twice or three times by -CN, -NO₂, -NR₅₅R₅₆, -CO₂R₅₇, -CONR₅₈R₅₉,

-COR₆o, -C(R₆ι)=NOR₆₂, -C(S)NR₆₃R₆ , -C(C C₄alkylthio)=NR₆₅, -OR₆₆, -SR₆₇, -SOR_68>

-SO₂R₆₉, -O(SO₂)R₇₀, -N(R₇₁)CO₂R₇₂₎ -N(R₇₃)COR₇₄ or C₃-C₆cycloalkyl; and/or each R₂ is independently C₂-C₈alkenyl, or C₂-C₈alkenyl substituted from one to five times by halogen or once, twice or three times by -CN, -NO₂, -CO₂R₇₅, -CONR₇₆R₇₇, -COR₇₈,

-C(R₇₉)=NOR₈₀, -C(S)NR₈ R₈₂, -C(C C₄alkylthio)=NR₈₃ or C₃-C₆cycloalkyl; and/or each R₂ is independently C₂-C₈alkynyl, or C₂-C₈alkynyl substituted from one to five times by halogen or once, twice or three times by -CN, -CO₂R₈₄, -CONR₈₅R₈₆, -COR₈₇, -

C(R₈₈)=NOR_89> -C(S)NR₉₀R₉₁, -C(C C₄alkylthio)=NR₉₂ or C₃-C₆cycloalkyl; and/or each R₂ is independently C₃-C₆cycloalkyl, or C₃-C₆cycloalkyl substituted from one to five times by halogen or once, twice or three times by -CN, -CO₂R₉₃, -CONR₉₄R₉₅, -COR₉₆,

-C(R₉₇)=NOR_98> -C(S)NR₉₉R₁₀₀ or -C(C C₄alkylthio)=NRιoι; and/or two adjacent R₂ together form a C C₇alkylene bridge, which may be interrupted by 1 or 2 non-adjacent oxygen atoms and substituted by d-C₆alkyl, the total number of ring atoms being at least 5 and at most 9; and/or two adjacent R₂ together form a C₂-C₇alkenylene bridge, which may be interrupted by 1 or 2 non-adjacent oxygen atoms and substituted by C C₆alkyl, the total number of ring atoms being at least 5 and at most 9; "

R₅₅ is hydrogen or d-C₈alkyl; R₅₆ is hydrogen, CrC₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by C C₄alkyl, C C₄haloalkyl, d-C₄alkoxy, -CN, -NO₂, d-C₄alkylthio, Cι-C₄- alkylsulfinyl or Cι-C₄alkylsulfonyl; or

R₅₅ and R₅₆ together are a C₂-C₅alkylene chain, which may be interrupted by an oxygen atom or a sulfur atom;

R₅₇ is hydrogen, C C₈alkyl, C₃-C₈alkenyl or C₃-C₈alkynyl, or d-C₈alkyl, C₃-C₈alkenyl or

C₃-C₈alkynyl substituted from one to five times by halogen or once, twice or three times by

Cι-C₄alkoxy or phenyl, wherein phenyl may itself be substituted from one to five times by halogen and/or once, twice or three times by Cι-C₄alkyl, d-C haloalkyl, C C₄alkoxy, -CN,

-NO₂, d-C alkylthio, d-C alkylsulfinyl or C C₄alkylsulfonyl;

R₅₈ is hydrogen or d-C₈alkyl;

R₅₉ is hydrogen or d-C₈alkyl, or d-C₈alkyl substituted once, twice or three times by -COOH, d-C₈alkoxycarbonyl or -CN; or

R₅₉ is C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by d-C₄alkyl, d-C₄haloalkyl, C C₄aIkoxy, -CN, -NO₂, d-C₄alkylthio, C C₄alkylsulfinyl or d-C₄alkylsulfonyl; or

R₅₈ and R₅₉ together are C₂-C₅alkylene;

R₆₀ is hydrogen, C C alkyl, Cι-C₄haloalkyl or C₃-C₆cycloalkyl;

R₆ι is hydrogen, C C alkyl, CrC haloalkyl or C₃-C₆cycloalkyl;

R₆₂ is hydrogen, C C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, C C haloalkyl or C₃-C₆haloalkenyl; and

R₆₃ is hydrogen or d-C₈alkyl;

Re₄ is hydrogen or d-C₈alkyl, or CrC₈alkyl substituted once, twice or three times by -COOH,

Cι-C₈alkoxycarbonyl or -CN; or

R₆₄ is C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by C C₄alkyl, C C₄haloalkyl, C C₄alkoxy, -CN, -NO₂, C C₄alkylthio, C_rC₄alkylsulfinyl or d-C₄alkylsulfonyl; or

R₆₃ and R₆₄ together are C₂-C₅alkylene;

R₆₅ is hydrogen or d-C₈alkyl;

R₆₆ and R₆₇ are each independently of the other hydrogen, d-C₈alkyl, C₃-C₈alkenyl or

C₃-C₈alkynyl, or C C₈alkyl substituted from one to five times by halogen or once, twice or three times by -CN or d-C alkoxy; R₆₈ R₈₉ and R₇₀ are each independently of the others C C₈alkyl, C₃-C₈alkenyl or C₃-C₈- alkynyl, or Cι-C₈alky! substituted from one to five times by halogen or once, twice or three times by -CN or Cι-C₄alkoxy;

R₇₁ and R₇₃ are each independently of the other hydrogen, d-C₈alkyl or C C₈alkoxy;

R₇₂ is d-C₈alkyl;

R₇ is hydrogen or Cι-C₈alkyl;

R₇₅ is hydrogen, or CrC₈alkyl, C₃-C₈alkenyl or C₃-C₈alkynyl each of which may be substituted from one to five times by halogen or once, twice or three times by d-C alkoxy or phenyl, wherein phenyl may itself be substituted from one to five times by halogen and/or once, twice or three times by C_rC₄alkyl, d-C₄haloalkyl, d-C₄alkoxy, -CN, -NO₂, d-C₄alkyl- thio, C C alkylsulfinyl or d-C₄alkylsulfonyl;

R₇₆ is hydrogen or d-C₈alkyl;

R₇₇ is hydrogen or CrC₈alkyl, or d-C₈alkyl substituted once, twice or three times by -COOH, d-C₈alkoxycarbonyl or -CN; or

R₇₇ is C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by d-C₄alkyl, C C₄haloalkyl, d-C₄alkoxy, -CN, -NO₂, d-C₄alkylthio, d-C alkylsulfinyl or d-C₄alkylsulfonyl; or

R₇₆and R₇₇ together are C₂-C₅alkylene;

R₇₈ and R₇₉ are each independently of the other hydrogen, CrC alkyl, Cι-C₄haloalkyl or

C₃-C₆cycloalkyl;

R₈₀ is hydrogen, d-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, C C₄haloalkyl or C₃-C₆haloalkenyl;

R₈ is hydrogen or d-C₈alkyl;

R₈₂ is hydrogen or Cι-C₈alkyl, or C C₈alkyl substituted once, twice or three times by -COOH, d-C₈alkoxycarbonyl or -CN; or

R₈₂ is C₃-C₈aikenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by C C₄alkyl, C C haloalkyl, C C₄alkoxy, -CN, -NO₂, C_rC₄alkylthio, C_rC₄alkylsulfinyl or d-C₄alkylsulfonyl; or

R₈₁ and R₈₂ together are C₂-C₅alkylene;

R₈₃ is hydrogen or d-C₈alkyl;

Rεw is hydrogen, or Cι-C₈alkyl, C₃-C₈alkenyl or C₃-C₈alkynyl each of which may be substituted from one to five times by halogen or once, twice or three times by d-C₄alkoxy or phenyl, wherein phenyl may itself be substituted from one to five times by halogen and/or once, twice or three times by d-C alkyl, C C haloalkyl, C C₄alkoxy, -CN, -N0₂, d-C₄alkyl- thio, Cι-C₄aikylsulfinyl or d-C₄alkylsulfonyl; R₈₅ is hydrogen or Cι-C₈alkyl;

R₈₈ is hydrogen or d-C₈alkyl, or d-C₈alkyl substituted once, twice or three times by -COOH, d-C₈alkoxycarbonyl or -CN; or

R₈₆ is C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by C C₄alkyl, d-C₄haloalkyl, C C₄alkoxy, -CN, -NO₂, C C₄alkylthio, d-C₄alkylsulfinyl or d-C₄alkylsulfonyl; or

R₈₅ and R₈₆ together are C₂-C₅alkylene;

R₈₇ is hydrogen, d-C alkyl, C C₄haloalkyl or C₃-C₆cycloalkyl;

R₈₈ is hydrogen, C C₄alkyl, d-C₄haloalkyl or C₃-C₆cycloalkyl;

R₈₉ is hydrogen, d-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, Cι-C₄haloalkyl or C₃-C₆haloalkenyl;

R₉₀ is hydrogen or d-C₈alkyl;

R₉₁ is hydrogen or d-C₈alkyl, or d-C₈alkyl substituted once, twice or three times by -COOH, d-C₈alkoxycarbonyl or -CN; or

R₉₁ is C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by C C₄alkyl, d-C₄haloalkyl, C C₄alkoxy, -CN, -NO₂, d-C₄alkylthio, C C₄alkylsulfinyl or d-C₄alkylsulfonyl; or

R₉₀ and R₉₁ together are C₂-C₅alkylene;

R₉₂ is hydrogen or Cι-C₈alkyl;

R₉₃ is hydrogen, or C-|-C₈alkyl, C₃-C₈alkenyl or C₃-C₈alkynyl each of which may be substituted from one to five times by halogen or once, twice or three times by d-C₄alkoxy or phenyl, wherein phenyl may itself be substituted from one to five times by halogen and/or once, twice or three times by C C₄alkyl, C C₄haloalkyl, CrC alkoxy, -CN, -NO₂, d-C₄alkyl- thio, C C₄alkylsulfinyl or C C alkylsulfonyl;

R₉₄ is hydrogen or Cι-C₈alkyl;

R₉₅ is hydrogen or d-C₈alkyl, or d-C₈alkyl substituted once, twice or three times by -COOH, d-C₈alkoxycarbonyl or -CN; or

R₉₅ is C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by C C₄alkyl, d-C₄haloalkyl, C C₄alkoxy, -CN, -NO₂, C C₄alkylthio, C_rC₄alkylsulfinyl or d-C₄alkylsulfonyl; or

R₉ and R₉₅ together are C₂-C₅alkylene;

R₉₆ is hydrogen, C C₄alkyl, C C₄haloalkyl or C₃-C₆cycloalkyl;

R₉₇ is hydrogen, Cι-C₄alkyl, Cι-C₄haloalkyl or C₃-C₆cycloalkyl;

R₉₈ is hydrogen, d-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, d-C₄haloalkyl or C₃-C₆haloalkenyl; R₉₉ is hydrogen or Cι-C₈alkyl;

R₁₀₀ is hydrogen or d-C₈alkyl, or d-C₈alkyl substituted once, twice or three times by

-COOH, C C₈alkoxycarbonyl or -CN; or

R₁₀₀ is C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by d-C₄alkyl, d-C₄haloalkyl, C C₄alkoxy, -CN, -NO₂, C_rC₄alkylthio, C C₄alkylsulfinyl or d-C₄alkylsulfonyl; or

R₉₉ and R₁₀o together are C₂-C₅alkylene; and

R₁0₁ is hydrogen or d-C₈alkyl, and to agrochemically acceptable salts and all stereoisomers and tautomers of compounds of formula I.

When n is 0, all free valencies on the phenyl ring of the compounds of formula I are occupied by hydrogen. When m is 0, all free valencies on the thienyl ring of the compounds of formula I are occupied by hydrogen.

Examples of substituents formed by R₅ and R₆ together, or R₁₈ and R₁₉ together, or R₃₆ and R₃₇ together, or R₅₅ and R_ε6 together denoting a C₂-C₅alkylene chain, which may be substituted by an oxygen atom or a sulfur atom, are piperidine, morpholine, thiomorpholine or pyrrolidine.

The alkyl groups appearing in the definitions of substituents may be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, and also the isomers of pentyl, hexyl, heptyl and octyl.

Alkenyl and alkynyl groups may likewise be straight-chain or branched, the same applying also to the alkyl, alkenyl and alkynyl moieties of hydroxyalkyl, cyanoalkyl, alkylcarbonyl, alkylcarbonylalkyl, alkoxycarbonyl, alkenyloxy-alkyl, alkynyloxy-alkyl, alkylthio-alkyl, alkoxyalkyl, alkylamino, dialkylamino and phenylalkyl and e.g. the groups -C(Rι₀)=NORn and -C(₆₁)=NOR₆₂.

Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine. Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloro- methyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1 ,1- difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl or 2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl or dichlorofluoromethyl. As haloalkenyl there come into consideration alkenyl groups substituted one or more times by halogen, halogen being in particular bromine or iodine and especially fluorine or chlorine, for example 2- and 3-fluoropropenyl, 2- and 3-chloropropenyl, 2- and 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl, 4,4,4-trifluoro-but-2-en-1 -yl and 4,4,4- trichloro-but-2-en-1-yl. Of the alkenyl radicals substituted from one to five times by halogen, preference is given to those having a chain length of 3 or 4 carbon atoms. The alkenyl groups can be substituted by halogen at saturated or unsaturated carbon atoms.

As haloalkynyl there come into consideration, for example, alkynyl groups substituted from one to five by halogen, halogen being bromine or iodine and especially fluorine or chlorine, for example 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoropropynyl and 4,4,4-trifluoro-but-2-yn-1-yl. Of the alkynyl radicals substituted from one to five times by halogen, preference is given to those having a chain length of from 3 to 5 carbon atoms.

Alkylcarbonyl is especially acetyl or propionyl.

Cyanoalkyl is, for example, cyanomethyl, cyanoethyl, cyanoeth-1 -yl or cyanopropyl.

Hydroxyalkyl is, for example, 2-hydroxyethyl, 3-hydroxypropyl or 2,3-dihydroxypropyl.

Alkoxy groups preferably have a chain length of from 1 to 6, especially from 1 to 4, carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy, or also the pentyloxy and hexyloxy isomers; preferably methoxy or ethoxy.

Alkoxy, alkenyl, alkynyl, alkoxyalkyl, alkylthio, alkylsulfonyl, alkylsulfinyl, alkylaminoalkoxy, alkoxycarbonyl, alkylcarbonyloxy, alkenylthio, alkenylsulfonyl, alkenylsulfinyl, alkynylsulfonyl, alkynylthio and alkynylsulfinyl groups are derived from the mentioned alkyl radicals. The alkenyl and alkynyl groups can be mono- or poly-unsaturated. Alkenyl is to be understood as being, for example, vinyl, allyl, methallyl, 1 -methylvinyl or but-2-en-1 -yl. Alkynyl is, for example, ethynyl, propargyl, but-2-yn-1-yl, 2-methylbutyn-2-yl or but-3-yn-2-yl.

Haloalkoxy is, for example, fluoromethoxy, difluoroethoxy, trifluoromethoxy, 2,2,2- trifluoroethoxy, 1,1 ,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy or 2,2,2- trichloroethoxy. Alkylthio groups preferably have a chain length of from 1 to 4 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio. Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl or tert-butylsulfinyl; preferably methylsulfinyl or ethylsulfinyl.

Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl; preferably methylsulfonyl or ethylsulfonyl.

Haloalkylsulfonyl is, for example, fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoro- methylsulfonyl, chloromethylsulfonyl, trichloromethylsulfonyl, 2-fluoroethylsulfonyl, 2,2,2- trifluoroethylsulfonyl or 2,2,2-trichloroethylsulfonyl.

Alkoxyalkyl groups have preferably from 1 to 6 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.

Alkylamino is, for example, methylamino, ethylamino and the propylamino and butylamino isomers.

Dialkylamino is, for example, dimethylamino, diethylamino and the dipropylamino and dibutylamino isomers.

The cycloalkyl radicals that come into consideration as substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

Corresponding meanings can also apply to the substituents in combined definitions, such as alkoxy-alkoxycarbonyl, alkoxycarbonylalkyl, cycloalkyl-alkyl, Rι₃O-, -C(R₂₄)=NOR₂₅, -alkyl- N(R₇₁)CO₂R₇₂, -C(Cι-C₄-alkylthio)=NR₆₅, -N(R₇₃)COR₇₄ and -N([CO]pR₄₉)COR₅₀.

Substituents wherein two adjacent Ri together form a d-C₇alky!ene bridge, which may be interrupted by 1 or 2 non-adjacent oxygen atoms and substituted by Cι-C₆alkyl, the total number of ring atoms being at least 5 and at most 9, and/or wherein two adjacent R_T together form a C₂-C₇alkenylene bridge, which may be interrupted by 1 or 2 non-adjacent oxygen atoms and substituted by Cι-C₆alkyl, the total number of ring atoms being at least 5 and at most 9, have, for example, the following structures:

Substituents wherein two adjacent R₂ together form a d-C₇alkylene bridge, which may be interrupted by 1 or 2 non-adjacent oxygen atoms and substituted by d-C₆alkyl, the total number of ring atoms being at least 5 and at most 9, and/or wherein two adjacent R₂ together form a C₂-C₇alkenylene bridge, which may be interrupted by 1 or 2 non-adjacent oxygen atoms and substituted by d-C₆alkyl, the total number of ring atoms being at least 5 and at most 9, have, for example, the following structures:

The invention relates also to the salts which the compounds of formula I are able to form especially with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases. Suitable salt-formers are described, for example, in WO 98/41089.

Among the alkali metal and alkaline earth metal hydroxides as salt formers, special mention should be made of the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially the hydroxides of sodium and potassium.

Examples of amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary Cι-C₁₈alkylamines, d-C₄hydroxyalkylamines and C₂-C₄- alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octyl- amine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octa- decylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyl- octylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n-propyl- amine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N- diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n- butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine.

Preferred quaternary ammonium bases suitable for salt formation correspond e.g. to the formula [N(R_a R_bR₀Rd )]OH wherein R_a, Rb, e and Rd are each independently of the others Cι-C₄alkyl. Other suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions.

Preferred compounds of formula I are those wherein each R^ is independently halogen, -CN, -NO₂, -C(R₁₀)=NOR₁₁, -OR₁₃, -SO₂R₁₆, -OSO₂R₁₇, d-C₈alkyl or C₂-C₈alkenyl, and/or C C₈- alkyl substituted from one to five times by halogen and/or once, twice or three times by -CN; R₁₀ is hydrogen or Cι-C₄alkyl; Ru is d-C₈alkyl; and R₁₃ is C C₄alkyl.

Further preferred compounds of formula I are those wherein each R₂ independently is halogen, -CN, -NO₂, -NR₃₆R₃₇, -CO₂R₃₈, -C(R₄ι)=NOR₄₂, -OR^,

-SO₂R₄₇, -OSO₂R ₈ or d-C₈alkyl, and/or d-C₈alkyl substituted from one to five times by halogen and/or once, twice or three times by -CN or -CO₂R₅₇;

R₃₆ and R₃₇ are hydrogen;

R₃₈ is hydrogen or d-C₈alkyl;

R₄₁ is hydrogen or d-C₄alkyl; and

R ₂ is d-C₈alkyl.

An especially preferred group of compounds of formula I comprises those wherein each Ri is independently halogen, -CN, -NO₂, -C(R₁₀)=NOR_{11 )} -OR₁₃, -SO₂R₁₆, -OSO₂R₁₇, C C₈alkyl or C₂-C₈alkenyl, and/or C C₈alkyl substituted once, twice or three times by -CN; R₁₀ is hydrogen or d-C₄alkyl;

Ru is d-C₈alkyl; and

R₁₃ is d-C₄alkyl; each R₂ is independently halogen, -CN, -NO₂, -NR₃₆R₃₇, -CO₂R₃₈, -C(R₄₁)=NOR₄₂, -OR ₄,

-SO₂R₄₇, -OSO₂R₄₈ or d-C₈aIkyl, and/or C C₈alkyl substituted once, twice or three times by

-CN or -CO₂R₅₇;

R₃₆ and R₃ are hydrogen;

R₃₈ is hydrogen or d-C₈alkyl;

R₄ι is hydrogen or d-C alkyl;

R₄₂ is d-C₈alkyl; and

R₃ and R₄ are each independently of the other hydrogen or d-C₄alkyl.

Also of interest are compounds of formula I wherein each R_! is independently halogen or -CN, and/or d-C₈alkyl substituted by -CN, and/or Cι-C₈alkoxy. Hereof of special interest are compounds wherein at least one of the substituents Ri is Cι-C₈alkyl substituted by -CN.

Preference is given to compounds of formula I wherein each R₂ is independently halogen or -CN, and/or d-C₈alkyl substituted by -CN, and/or d-C₈alkoxy. Hereof of special preference are compounds wherein at least one of the substituents R₂ is d-C₈alkyl substituted by -CN.

Preference is given also to compounds of formula I wherein n is 0, 1 or 2 and m is 0, 1 or 2, n being especially 1 or 2 and m being especially 1 or 2.

Of special interest are compounds of formula I wherein R₃ and R₄ are hydrogen.

Special mention should also be made of compounds of formula I wherein R^ is hydrogen, halogen, methoxy, difluoromethoxy, trifluoromethyl or cyano-Cι-C₈alkyl;

R₂ is cyanomethyl, chlorine or bromine;

R₃ and R are hydrogen; n is 1 or 2, and m is 1.

The compounds of formula I can be prepared by methods known per se described, for example, in K. Sonogashira, Comprehensive Organic Synthesis 1991 , Vol. 3, page 521 ft; G. W. Gribble et al, Palladium in Heterocyclic Chemistry 2000(20), 254-256; J. Chem. Soc, Perkin Trans I, 2000(5), 775; and Synth. Communic. 1990(20), 2059-2064, for example by reacting a compound of formula II

wherein R^ and n are as defined for formula I, in the presence of a base, with a compound of formula III

wherein R₃ and R₄ are as defined for formula I and X-j is O-tosyl, (-OTs), -OH, chlorine, bromine or iodine, to form a compound of formula IV

wherein R_1; R₃, R₄ and n are as defined for formula I, and then coupling that compound with a compound of formula V

wherein R₂ and m are as defined for formula I and A is a leaving group, e.g. halogen or trifluoromethanesulfonate, in the presence of a palladium catalyst.

The preparation of the compounds of formula I can be carried out e.g. according to Schemes 1 , 2, 3, 4, 5 and 6. For the individual synthesis Schemes it is generally true that various substituents R_! and/or R₂ are either already present at the outset or can be introduced in succession, for example by nucleophilic substitution.

According to Reaction Scheme 1 , the compounds of formula I can be obtained, for example, from substituted phenyl propargyl ethers of formula IV. The propargyl ethers of formula IV can be obtained beforehand by alkylation of phenols of formula II, which are reacted in the presence of a base with acetylene derivatives of formula III wherein Xi is halogen, for example chlorine, bromine or iodine, or -O-tosyl, (route a) in Reaction Scheme 1). Such alkylation reactions are standard procedures and can be carried out e.g. analogously to Tetrahedron 1997 (53), 12621-12628; Helv. Chim. Acta 2000 (83), 650-657; Chem. Ber. 1980(113), 261; and J. Chem. Res., Synop. 1996(10), 462-463.

A further method by which the compounds of formula IV can be prepared is carried out by the Mitsunobu reaction in the presence of azadicarboxylic acid diethyl ester (DEAD) and triphenylphosphine in a solvent, e.g. an ether, for example tetrahydrofuran (THF) analogously to the method described in Synthetic Communic. 1989(19), 1255-1259 (route b) in Reaction Scheme 1.

In the next step, the propargyl ethers of formula IV are coupled with substituted thiophenes of formula V under typical Sonogashira conditions (K.Sonogashira, Comprehensive Organic Synthesis, 1991 , Vol. 3, page 521 ff.). Catalyst mixtures that come into consideration are, for example, tetrakis(triphenylphosphine)palladium or bistriphenylphosphinepalladium dichloride together with copper iodide, and bases that come into consideration are especially amines, for example triethylamine, diethylamine, diisopropylethylamine or piperidine, and carbonates, especially sodium or potassium carbonate.

The thiophenes of formula V preferably carry a leaving group A, wherein A is e.g. halogen (J. Chem. Soc, Perkin Trans I, 2000. 775-779; and Synthetic Communic. 1990(20), 2059- 2064) or, analogously to benzene derivatives as described in Tetrahedron Lett. 1986(27), 1171-1174, is trifluoromethanesulfonate. As solvents there are customarily used ethers, for example tetrahydrofuran, chlorinated hydrocarbons, for example chloroform, or dipolar aprotic solvents, for example dimethylformamide or dimethyl sulfoxide. Reaction Scheme 1

Sonogashira coupling:

The Pd-catalysed cross-coupling of suitably substituted thiophenes of formula V with propargyl alcohols or terminal acetylenes of formula III wherein X₁ is OH is generally known as the Sonogashira reaction (Reaction Scheme 2). That reaction has already been illustrated in detail in Reaction Scheme 1 and can likewise be used for the preparation of the thienylpropargyl alcohols of formula VII

wherein R₂, R₃, R₄ and m are as defined for formula I and X, is OH.

The activation of the alcohol of formula VII to form the compounds of formula VIII wherein X₁ is halogen, tosylate (-OTs) or triflate (-OC(O)CF₃) is carried out e.g. by tosylation or halogenation.

The tosylation of the alcohol of formula VII is a standard reaction and can be carried out e.g. with a sulfonic acid chloride, for example mesyl chloride or para-toluenesulfonic acid chloride (p-TsCI), in the presence of an amine, for example diethylamine, triethylamine or pyridine, in a solvent, e.g. a chlorinated hydrocarbon, for example carbon tetrachloride or methylene chloride, or an amine, for example pyridine. Such reactions are generally known and are described e.g. in J. Org. Chem. 1997, 62, page 8987; J. Het. Chem. 1995, 32, pages 875- 882; and also in Tetrahedron Lett. 1997, 38, pages 8671 -8674.

The halogenation can be carried out analogously to standard procedures. For example, the bromination is carried out with carbon tetrabromide in the presence of triphenylphosphine (Synthesis 1998, pages 1015-1018) in methylene chloride. The chlorination is carried out with mineral acids, for example with concentrated hydrochloric acid (J. Org. Chem. 1955 (20), page 95) or with para-toluenesulfonic acid chloride in the presence of an amine, for example triethylamine, in a solvent, e.g. methylene chloride (Tetrahedron Lett. 1984 (25), page 2295).

The preparation of the thienyl-propynyloxy-benzenes of formula I according to Reaction Scheme 2, route c) can be effected using the phenols of formula II as starting materials by reaction with compounds of formula VIII

wherein R₂, R₃, R₄ and m are as defined above and ^ is halogen, -OTs or -OC(O)CF₃, in the presence of a base, analogously to the method described e.g. in J. Chem. Research (S), 1996, 462; or Helv. Chim. Acta 1985(68), 355. Using the same phenols of formula II and the compounds of formula VIII as starting materials, etherification to form the thienyl-propynyloxy-benzenes of formula I according to route d) in Reaction Scheme 2 is effected also by means of copper iodide-catalysed reaction analogously to Synthesis 1995, 707-712; Tetrahedron Lett. 1994 (35), 6405-6408; and WO 00/18754.

Suitable solvents for route d) are dimethylformamide or acetonitrile, and suitable bases are especially potassium carbonate or 1 ,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

Reaction Scheme 2

Sonogashira:

V: A = halogen, O-SO₂-CF₃ VII: X₁₌OH VIII: X_Ϊ = halogen, -OTs, -OC(O)CF₃

Compounds of formula I can also be obtained according to other methods, as illustrated, for example, in Reaction Scheme 3. Reaction Scheme 3 Sonogashira:

V: A = Br, I, ~0-SO,CF

V: A = Br, I, -0-S

reduction or Grignard reagents

VIII: X_{1 =} halogen, -OTs Accordingly, thiopheneacetylene esters of formula X

wherein R₂ and m are as defined for formula I, are obtained by Sonogashira coupling from compounds of formula IXa or IXb

^IXa °^r (C₁-C₄alkylO)₃C — C≡CH IXb

and activated thiophene derivatives of formula V are obtained analogously to Synthetic Communic. 1998(28), 327-335; and Synthesis 1992, 746-748. The esters of formula X can then be reduced, or reacted with organometallic compounds, for example Grignard reagents, to form the alcohols of formula VII wherein X₁ is OH.

The reduction can be carried out especially with hydrides by standard methods, for example with lithium aluminium hydride or sodium borohydride in a solvent, e.g. an ether, for example diethyl ether, dioxane or tetrahydrofuran, or an alcohol, for example methanol or ethanol. Such reductions are described e.g. in C. Ferri, "Reaktionen der organischen Synthese" 1978, pages 98-102.

Reactions of carboxylic acid esters with Grignard reagents are standard in organic synthetic chemistry and are described in detail, for example, in "Organikum" 1976, pages 617-625. The subsequent etherification of the phenol derivatives of formula II in the presence of compounds of formula VIII to form the compounds of formula I has already been described in detail in Reaction Scheme 2.

In addition, the desired target compound of formula I can also be obtained by the Mitsunobu reaction by direct reaction of a compound of formula VII wherein ^ is OH with a phenol of formula II.

Further methods of preparing the desired target compounds of formula I are shown in Reaction Scheme 4 (variant of Reaction Scheme 3). Reaction Scheme 4

XI

reduction, e.g. LiAIH₄ or organometal compounds, e.g. Grignard reagents

Vl X^OH

The reaction of thienylacetylenes of formula XI

wherein R₂ and m are as defined for formula I, with chloroformates of formula XII d-C₄alkylOC(O)CI (XII) according to route e) in Reaction Scheme 4, is carried out in the presence of catalytic amounts of a palladium catalyst, for example tetrakis(triphenylphosphine)palladium (Pd[P(C₆H₅)₃]₄), analogously to J. Chem. Soc. Perkin Trans 1, 1994(24), 3555-3556, and yields the desired ester of formula X. According to route f) in Reaction Scheme 4, the ester of formula X can also be obtained by reaction of the thienylacetylene of formula XI with carbon monoxide and with the alcohol of formula XIII d-C₄alkyl-OH (XIII) in the presence of palladium catalysts and coρper(ll) chloride (CuCl₂). That reaction is carried out analogously to that described in Synth. Communic. 1994(24), 85-88. The ester of formula X can be converted into the desired target compound of formula I entirely analogously to the method already described in Reaction Scheme 3, via an alcohol of formula VII wherein X-, is OH.

The nucleophilic aromatic substitution of the activated phenyl halides of formula XIV

wherein X₂ is halogen, n is 1 , 2, 3, 4 or 5, and R-, is a substituent having an electron- withdrawing effect (-M and/or -I effect), e.g. -NO₂, -CN, -CF₃ or COR₁₂, with the propargyl alcohols of formula VII wherein Xi is OH to form compounds of formula I is illustrated in Reaction Scheme 5 and can be carried out analogously to known methods, as described, e.g., in Synlett 2000(6), 874-876; ibid. 1998(7), 794-796. Accordingly, the activated phenyl halide of formula XIV is reacted with a propargyl alcohol of formula VII wherein X-i is OH in an aprotic solvent, e.g. an amide, for example N,N-dimethylformamide (DMF) or 1-methyl-2- pyrrolidone (NMP), a sulfoxide, for example dimethyl sulfoxide (DMSO), a ketone, for example acetone, or an ether, for example tetrahydrofuran (THF), in the presence of a base, e.g. a carbonate, for example potassium or cesium carbonate, or a metal hydride, for example sodium hydride, at temperatures of from 0°C to 100°C. Reaction Scheme 5 nucleophilic aromatic substitution:

su st tuent av ng a - an or - e ect

Compounds of formula I can also be prepared by first reacting propargyl alcohols of formula III wherein R₃ and R are as defined for formula I and X, is OH with activated phenyl halides of formula XIV to form compounds of formula IV, and only then, in the next synthesis step, carrying out a Sonogashira reaction with activated thiophene derivatives of formula V (Reaction Scheme 6).

Reaction Scheme 6

nucleophilic aromatic substitution:

XIV: χ₂ = halogen, and R₁ is a IV substituent having a -M and/or -I effect

Sonogashira coupling:

The following comments apply to the individual reaction steps in Reaction Schemes 1 to 6: The reactions to form compounds of formula I are advantageously performed in aprotic, inert organic solvents. Such solvents are hydrocarbons, such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons, such as dichloromethane, trichloromethane, tetra- chloromethane or chlorobenzene, ethers, such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles, such as acetonitrile or propionitrile, amides, such as N,N-dimethylformamide, diethylformamide or N- methylpyrrolidinone. The reaction temperatures are preferably from -20°C to +120°C. The reactions generally proceed slightly exothermically and can usually be carried out at room temperature. In order to shorten the reaction time or alternatively to initiate the reaction, the reaction mixture may, if appropriate, be heated, up to its boiling point, for a short time. The reaction times may likewise be shortened by the addition of a few drops of base as reaction catalyst. Suitable bases are especially tertiary amines, such as trimethylamine, triethylamine, quinuclidine, 1 ,4-diazabicyclo[2.2.2]octane, 1 ,5-diazabicyclo[4.3.0]non-5-ene and 1 ,5-diaza- bicyclo[5.4.0]undec-7-ene, but it is also possible to use inorganic bases, such as hydrides, e.g. sodium or calcium hydride, hydroxides, such as sodium or potassium hydroxide, carbonates, such as sodium or potassium carbonate, or hydrogen carbonates, such as potassium or sodium hydrogen carbonate.

The compounds of formula I can be isolated in customary manner by concentration and/or evaporation of the solvent and can be purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons.

The starting compounds of formulae II used in Reaction Scheme 1 to prepare compounds of formula I are mostly known, or can be prepared analogously to known methods.

The starting compounds and reagents of formulae III, V, IXa, IXb, XI, XII, XIII and XIV used in Reaction Schemes 1 to 6 are likewise known, in some cases are commercially available or can be prepared analogously to known methods.

For the use according to the invention of the compounds of formula I, or of compositions comprising them, there come into consideration all methods of application customary in agriculture, for example pre-emergence application, post-emergence application and seed dressing, and also various methods and techniques such as, for example, the controlled release of active ingredient. For that purpose a solution of the active ingredient is applied to mineral granule carriers or polymer granules (urea/formaldehyde) and dried. If required, it is possible in addition to apply a coating (coated granules) that allows the active ingredient to be released in metered amounts over a specific period of time.

The compounds of formula I can be used as herbicides in their unmodified form, that is to say as obtained in the synthesis, but they are preferably formulated in customary manner together with the adjuvants conventionally employed in formulation technology, for example into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. Such formulations are described, for example, on pages 9 to 13 of WO 97/34485. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.

The formulations, that is to say the compositions, preparations or mixtures comprising the compound (active ingredient) of formula I or at least one compound of formula I and, usually, one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with the formulation adjuvants, for example solvents or solid carriers. Surface-active compounds (surfactants) may also be used in addition in the preparation of the formulations. Examples of solvents and solid carriers are given, for example, on page 6 of WO 97/34485.

Depending upon the nature of the compound of formula I to be formulated, suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties. Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO 97/34485. In addition, the surfactants conventionally employed in formulation technology, which are described, inter alia, in "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981 , Stache, H., "Tensid-Taschen- buch", Carl Hanser Verlag, Munich/Vienna 1981 , and M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-81 , are also suitable for the preparation of the herbicidal compositions according to the invention.

The herbicidal formulations generally contain from 0.1 to 99% by weight, especially from 0.1 to 95% by weight, of herbicide, from 1 to 99.9%. by weight, especially from 5 to 99.8% by weight, of a solid or liquid formulation adjuvant, and from 0 to 25% by weight, especially from 0.1 to 25% by weight, of a surfactant. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations. The compositions may also comprise further ingredients, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), anti-foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.

The compounds of formula I are generally applied to plants or the locus thereof at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kg/ha. The concentration required to achieve the desired effect can be determined by experiment. It is dependent on the nature of the action, the stage of development of the cultivated plant and of the weed and on the application (place, time, method) and may vary within wide limits as a function of those parameters.

The compounds of formula I are distinguished by herbicidal and growth-inhibiting properties, allowing them to be used in crops of useful plants, especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non-selective weed control. The term "crops" is to be understood as including also crops that have been made tolerant to herbicides or classes of herbicides as a result of conventional methods of breeding or genetic techniques. The weeds to be controlled may be either monocotyl- edonous or dicotyledonous weeds, such as, for example, Steliaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.

The following Examples further illustrate but do not limit the invention.

Preparation Examples:

Example P1 : Preparation of 4-fluoro-2-methoxy-(prop-2-vnyloxy)-benzene

56.0 g (0.392 mol) of 4-fluoro-2-methoxy-phenol are dissolved at 20°C in N,N-dimethyl- formamide (DMF). 56.0 g (0.406 mol) of potassium carbonate are then added and the mixture is stirred for 1 hour at 20°C and then, in the course of about 15 minutes, 65.8 ml (0.77 mol, 80% solution in toluene) of propargyl bromide are added thereto and the reaction mixture is stirred for 18 hours at 50°C. 28.0 g of potassium carbonate are subsequently added and stirring is continued for a further 24 hours at 50°C. In order to complete the reaction, a further 25.6 g of potassium carbonate and 13.2 ml of propargyl bromide are added and the reaction mixture is stirred for a further 72 hours at 50°C. After filtration and removal of the solvent by evaporation, the residue is taken up in diethyl ether and 1 N sodium hydroxide solution (NaOH). The organic phase is separated off, washed three times in each case with water and sodium chloride solution and dried over sodium sulfate. The crude product is purified by chromatography on silica gel (eluant: ethyl acetate/hexane 1/5). 53 g of the title compound, 4-f!uoro-2-methoxy-(prop-2-ynyloxy)-benzene, are obtained in the form of a light-yellow oil.

¹H-NMR (CDCI₃) : δ (ppm) = 2.50 (t, 1 H); 3.85 (s, 3H); 4.70 (d, 2H); 6.55-6.70 (m, 2H); 6.95- 7.00 (m, 1H). Example P2: Preparation of (2-r3-(4-fluoro-2-methoxy-phenoxy)-prop-1-ynyl]-thiophene)-5- carbaldehvde

Under argon, 0.96 g (5 mmol) of 2-bromothiophene-5-carboxyaldehyde, 0.175 g (0.29 mmol) of palladium bis(triphenylphosphine) dichloride (Pd(PPh₃)₂Cl₂) and 0.05 g (0.29 mmol) of copper iodide (Cul) are introduced at 20°C into a solution of 12 ml of DMF and 6 ml of triethylamine. The mixture is then heated to 90°C and then very slowly, in the course of 2 hours, a solution, saturated with argon, of 1.35 g (7.5 mmol) of 4-fluoro-2-methoxy-(prop-2- ynyloxy)-benzene (Example P1 ) in 5 ml of DMF is added dropwise with stirring. After the addition, stirring is continued for 1 hour. After cooling to 20°C, the mixture is poured into 120 ml of saturated ammonium chloride solution and, after stirring briefly, extracted three times with ethyl acetate. The organic phases are combined and washed twice with ammonium chloride solution, twice with water and twice with sodium chloride solution. After drying over sodium sulfate, the crude product is subjected to flash chromatography on silica gel (eluant (gradient): ethyl acetate/hexane 1/6 to 1/4). 0.6 g of the title compound, 2-[3-(4- f luoro-2-methoxy-phenoxy)-prop-1 -ynyl]-thiophene-5-carbaldehyde, is obtained in crystalline form.

¹H-NMR (CDCI₃) : δ (ppm) = 3.70 (s, 3H); 4.80 (s, 2H); 6.40-6.60 (m, 2H); 6.80-6.90 (m, 1 H); 7.10 (d, 1 H); 7.48 (d, 1 H); 9.70 (s, 1 H).

Example P3: Preparation of f5-F3-(2-methoxy-phenoxy)-prop-1-vnvn-thiophen-2-yl|- acetonitrile

0.50 g (3.1 mmo of 1-methoxy-2-prop-2-ynyloxy-benzene see 01 55066), 0.77 g

(3.1 mmol) of (5-iodo-thiophen-2-yl)-acetonitrile (preparation analogous to US-A-5 580989), 0.01 g (0.014 mmol) of Pd(PPh₃)₂CI₂ and 0.01 g (0.053 mmol) of copper iodide (Cul) are dissolved at 20°C in 30 ml of diisopropylamine under argon. After stirring for about

30 minutes, the reaction is complete. The crude product is purified on silica gel by flash chromatography (eluant: ethyl acetate/hexane 1/5). 0.53 g of the title compound, {5-[3-(2- methoxy-phenoxy)-prop-1 -ynyl]-thiophen-2-yl}-acetonitrile, is obtained in solid form having a melting point of 73-75°C.

¹H-NMR (CDCI₃) : δ (ppm) = 3.85 (s, 2H); 3.90 (s, 3H); 4.95 (s, 2H); 6.90-7.15 (m, 6H).

Example P4: Preparation of 2-iodo-5-thienyl-acetonitrile

A mixture of 15.4 g (0.125 mol) of 2-thienyl-acetonitrile, 40 ml of acetic acid, 15 ml of water, 7 ml of concentrated sulfuric acid, 10 ml of carbon tetrachloride, 10.2 g (0.04 mol) of iodine and 4.1 g (0.023 mol) of iodic acid (HIO₃) is, in analogy to J. Med. Chem. 42(18), 3557 (1999), stirred at 20°C for 20 hours. Gas chromatography analysis shows that about 90% of the starting materials have reacted. After further addition of carbon tetrachloride, the organic phase is separated off and the aqueous phase is extracted with ethyl acetate. The organic phases are combined and washed with sodium thiosulfate solution and sodium chloride solution. After concentration of the dried organic phase, the crude product obtained is stirred in diethyl ether/hexane. The desired title compound is obtained in a yield of 18.5 g (60% of theory) in the form of light-brown crystals. ¹H-NMR (CDCI₃): δ(ppm)=3.88 (s, 2H); 6.75 (d, 1 H); 7.15 (d, 1 H).

Example P5: Preparation of 2-iodo-4-thienyl-acetonitrile

A mixture is prepared from 1.23 g (0.01 mol) of 3-thienyl-acetonitrile, 2.25 g (0.01 mol) of N-iodosuccinimide (NIS), 392 mg (0.001 mol) of Koser's reagent [hydroxy-(tosyloxy)-iodo]- benzene (Fluka 56517) and 50 ml of methanol and stirred for 3 hours at 20°C. 200 ml of diethyl ether are then added and the resulting mixture is subsequently washed with an aqueous solution of 5 g of sodium thiosulfate in 100 ml of water. The organic phase is separated off and treated with 100 ml of water and then with 100 ml of sodium chloride solution and concentrated by evaporation. The residue is purified by HPLC (eluant (gradient): ethyl acetate/hexane, 8-100% ethyl acetate in 16 minutes). The desired title compound is obtained in a yield of 2.2 g (88% of theory) in the form of a light-coloured oil.

Example P6: Preparation of {5-f3-(4-fluoro-2-methoxy-phenoxy)-prop-1 -ynvπ-thiophen-2-yll- acetonitrile

Under argon, 1.0 g (4.0 mmol) of 2-iodo-5-thienyl-acetonitrile (Example P4), 0.14 g (0.2 mmol) of palladium bis(triphenylphosphine) dichloride (Pd(PPh₃)₂CI₂) and 0.04 g (0.2 mmol) of copper iodide (Cul) are introduced at 20°C into a solution of 20 ml of N,N- dimethylformamide (DMF) and 10 ml of triethylamine. A solution, saturated with argon, of 1.1 g (6.0 mmol) of 4-fluoro-2-methoxy-(prop-2-ynyloxy)-benzene (Example P1) in 5 ml of DMF is then added dropwise over a period of 30 minutes with stirring (slightly exothermic reaction). After the addition of the acetylene compound, the mixture is then stirred for 2.5 hours. Analytical thin-layer chromatography indicates that starting materials are no longer present. The reaction mixture obtained is poured into 200 ml of saturated ammonium chloride solution and, after stirring briefly, extracted with ethyl acetate. The organic phases are combined and washed three times in each case with saturated ammonium chloride solution, water and brine. After drying over magnesium sulfate, the solvent is evaporated off. The resulting brown, oily residue is subjected to flash chromatography on silica gel (eluant: ethyl acetate/hexane 1/4). The desired target compound is obtained in the form of a dark, red-yellow oil. Example P7: Preparation of 3-r(4-fluoro-2-methoxy-phenoxy)-prop-1 -vnyll-2-(5- methyleneiminomethoxyHhiophene

A mixture of 400 mg (1.38 mmol) of {2-[3-(4-fluoro-2-methoxy-phenoxy)-prop-1-ynyl]- thiophene}-5-carbaldehyde (Example P2), 127 mg (1.52 mmol) of O-methylhydroxylamine hydrochloride and 10 ml of pyridine is heated at 120°C for 2 hours. The reaction mixture is then allowed to cool to 20°C and poured onto ice/hydrochloric acid 1/1. The crude product is obtained after extraction with ethyl acetate, washing the combined organic phases with water and sodium chloride solution, drying, and concentrating the solvent. It is purified by flash chromatography (eluant: ethyl acetate/hexane 1/7) to yield 0.430 mg of the desired title compound in the form of a resin and as a (syn/anti) isomeric mixture.

Example P8: Preparation of f3-(4-f luoro-2-methoxy-phenoxy)-prop-1 -vnyr|-2-(5- methyleneiminohydroxyHhiophene

A mixture of 400 mg (1.38 mmol) of 2-[3-(4-fluoro-2-methoxy-phenoxy)-prop-1-ynyl]- thiophene-5-carbaldehyde (Example P2), 106 mg (1.52 mmol) of hydroxylamine hydrochloride and 10 ml of pyridine is stirred at 120°C for 2 hours. After cooling, the reaction mixture is poured onto ice/hydrochloric acid 1/1 and the crude product is extracted with ethyl acetate. The combined organic phases are washed with water and then with sodium chloride solution, dried and concentrated by evaporation. Purification by flash chromatography (eluant: ethyl acetate/hexane 1/3) yields 403 mg of the desired title compound having a melting point of 89-90°C. Example P9: Preparation of f3-(4-fluoro-2-methoxy-phenoxy)-prop-1-vnyl]-2-(5- difluoromethvπ-thiophene

967 mg (6.0 mmol) of diethylamino-sulfur trifluoride (DAST) in 10 ml of absolute dichloromethane are introduced into a reaction vessel and, at from 0 to 5°C, a solution of 1.451 g (5.0 mmol) of 2-[3-(4-f luoro-2-methoxy-phenoxy)-prop-1 -ynyl]-thiophene-5- carbaldehyde (Example P2) in 5 ml of absolute dichloromethane is added dropwise. Stirring is then carried out for 4 hours at 20°C. After that time, analytical gas chromatography indicates complete conversion. After pouring the reaction mixture onto ice/water, the organic phase is separated off and the aqueous phase is extracted with dichloromethane. The combined organic phases are washed with water, then with 0.5N hydrochloric acid solution and subsequently with sodium chloride solution, dried and concentrated by evaporation. Purification by HPLC (eluant (gradient): ethyl acetate/hexane, 5-100% ethyl acetate in 8 minutes) yields the desired title compound in a yield of 713 mg in the form of a dark-brown oil.

Example P10: Preparation of 2-iodo-4-thienyl-acetonitrile

0.65 ml of concentrated (98%) sulfuric acid in 40 ml of acetic acid is added to a solution of 9.85 g (8.0 mmol) of thiophene-3-acetonitrile in 15 ml of water and 20 ml of carbon tetrachloride. 3.5 g (20 mmol) of iodic acid (HIO₃) and then 9.5 g (37.5 mmol) of iodine are added to the reaction mixture obtained, and the resulting dark-red mixture is then stirred for 21 hours at 20°C. The course of the reaction is monitored by gas chromatography (GC). Once all starting material has reacted, 100 ml of chloroform are added and the organic phase is separated off. The separated-off aqueous phase is extracted with three portions of chloroform. The combined organic phases are washed in succession with 0.5M sodium thiosulfate solution (Na₂S₂O_{3 aq}), saturated sodium hydrogen carbonate solution and sodium chloride solution and dried over magnesium sulfate and the solvent is evaporated off. The desired title compound is obtained after flash chromatography (eluant: ethyl acetate/hexane 1/20) in a yield of 9.3 g in the form of a light-coloured oil.

Example P11 : Preparation of {4-r3-(4-fluoro-2-methoxy-phenoxy)-prop-1-vnylHhiophen-2-yl)- acetonitrile

A solution of 20 ml of piperidine and 1.245 g (5.0 mmol) of 2-iodo-4-thienyl-acetonitrile (Example P5) is placed under argon at 20°C and stirred for 30 minutes. 0.289 g (0.25 mmol) of palladium-tetrakis(triphenylphosphine) (Pd(PPh₃)₄) is then added and stirring is continued for 1 hour. A solution, saturated with argon, of 0.991 g (5.5 mmol) of 4-fluoro-2-methoxy- (prop-2-ynyloxy)-benzene (Example P1) in a small amount of piperidine is subsequently added, with stirring, and immediately thereafter 0.082 g (0.43 mmol) of copper iodide (Cul) is added (exothermic reaction). Using an ice bath, the reaction temperature is maintained at 60°C until the temperature begins to fall again. After the addition of the acetylene compound, stirring is carried out for 2 hours. Analytical thin-layer chromatography indicates that starting materials are no longer present. The reaction mixture obtained is poured into 2 litres of saturated ammonium chloride solution and, after stirring briefly, extracted with diethyl ether. The combined organic phases are washed twice in each case with saturated ammonium chloride solution, water and sodium chloride solution. After drying over magnesium sulfate, the solvent is evaporated off and the residue obtained is purified by flash chromatography (eluant: ethyl acetate/hexane 1/5). The desired target compound is obtained in a yield of 950 mg in the form of a dark-yellow oil. Example P12: Preparation of (4-r3-(4-chloro-2-methoxy-phenoxy)-prop-1 -vnyll-thiophen-2- ylj-acetonitrile

Starting from 20 ml of piperidine, 1.245 g (5.0 mmol) of 2-iodo-4-thienyl-acetonitrile (Example P5), 0.289 g (0.25 mmol) of Pd(PPh₃)₄, 0.082 g (0.43 mmol) of copper iodide and 1 .081 g (5.5 mmol) of 4-chloro-2-methoxy-(prop-2-ynyloxy)-benzene, the above title compound is obtained analogously to Example P1 1 in a yield of 710 mg in the form of a dark-coloured oil.

Example P13: Preparation of (4-r3-(4-trifluoromethyl-2-methoxy-phenoxy)-prop-1-vnyll- thiophen-2-yl|-acetonitrile

Starting from 20 ml of piperidine, 1 .245 g (5.0 mmol) of 2-iodo-4-thienyl-acetonitrile (Example PS), 0.289 g (0.25 mmol) of Pd(PPh₃)₄, 0.082 g (0.43 mmol) of copper iodide and 1 .266 g (5.5 mmol) of 4-trifluoromethyl-2-methoxy-(prop-2-ynyloxy)-benzene in a small amount of piperidine, the above title compound is obtained analogously to Example P11 in a yield of 385 mg in the form of a light-brown oil.

Example P14: Preparation of {2-r3-(4-fluoro-2-methoxy-phenoxy)-prop-1 -vnyll-thiophenel-4- carbaldehyde

0.64 g (3.35 mmol) of 2-bromothiophene-4-carboxaldehyde, 0.117 g (0.1675 mmol) of Pd(PPh₃)₂Cl₂ and 0.032 g (0.1675 mmol) of Cul are introduced, under argon, into a solution of 8 ml of DMF and 4 ml of triethylamine and, with stirring, argon gas is passed through for a period of 45 minutes. A solution, saturated with argon, of 0.905 g (5.02 mmol) of 4-fluoro-2- methoxy-(prop-2-ynyloxy)-benzene (Example P1 ) in DMF is then slowly added dropwise in the course of 1 .5 hours at 90°C with stirring. After the addition, stirring is continued for 2 hours. After cooling to 20°C, 90 ml of saturated ammonium chloride solution are added and the resulting mixture is stirred for 15 minutes. The crude product is extracted with ethyl acetate (3 x 50 ml), and the combined organic phases are washed twice with saturated ammonium chloride solution and twice in each case with water and sodium chloride solution, and dried over magnesium sulfate. After evaporation, the crude product obtained is purified by silica gel chromatography (eluant: ethyl acetate/hexane 1/4). The desired title compound is obtained in a yield of 0.230 g (24% of theory) in the form of an orange resin.

It is also possible for the preferred compounds listed in the following Tables to be obtained in a manner analogous to that described in Examples P1 to P14, or in accordance with the methods shown in Reaction Schemes 1 to 6 and in the mentioned references. In the "Phys. Data" column, the temperatures indicated denote the melting point (m.p.) of the compounds in question. In those cases where the purity of the compounds has been investigated by HPLC/MS (High Pressure Liquid Chromatography/Electrospray Mass Spectrometry), the "Phys. Data" column indicates the [M+H]⁺ peak from Electrospray MS for the compound in question (e.g. Comp. No. 1.130).

Comp. Rt R₂ R₃ R₄ Phys. Data

No. m.p. (°C)

1.001 H 4-CI H H

1.002 H 4-CH₂CN H H

1.003 H 4-CH₂CN CH₃ H

1.004 2-OCH₃ 5-CN H H 84-85

1.005 2-F 4-CH₂CN H H

1.006 2-CI 4-CH₂CN H H Comp. RA R₂ R3 R₄ Phys. Data

No. m.p. (°C)

1.007 4-CI 4-CH₂CN H H

1.008 4-Br 4-CH₂CN H H

1.009 2-F, 4-F 4-CH₂CN H H

1.010 2-CI, 4-CI 4-CH₂CN H H

1.011 2-F, 4-CI 4-CH₂CN H H

1.012 2-F, 4-CI 4-CH₂CN CH₃ H

1.013 2-F, 4-CI 4-CH₂CN CH₃ CH₃

1.014 2-OCH₃, 4-CF₃ 4-CH₂CN H H oil

1.015 2-OCH₃, 4-F 4-CH₂CN H H oil

1.016 2-OCH₃, 4-CI 4-CH₂CN H H oil

1.017 2-OCH₃, 4-Br 4-CH₂CN H H

1.018 2-OCH₃, 4-F 4-CH₂CN CH₃ H

1.019 2-OCH₃, 4-CI 4-CH₂CN CH₃ H

1.020 2-OCH₃₎ 4-F 4-CH(CH₃)CN H H

1.021 2-OCH₃, 4-CI 4-CH(CH₃)CN H H

1.022 2-OCH3, 4-CH3 4-CH₂CN H H

1.023 2-OCH3, 4-CH3 4-CH(CH₃)CN H H

1.024 2-OCHF₂, 5-CH₃ 4-CH₂CN H H

1.025 2-OCHF₂, 4-CI 4-CH₂CN H ^" H

1.026 2-OCHF₂, 4-F 4-CH₂CN H H

1.027 2-OCH_3, 4-CH₂CN H H 4-CH=NOCH₃

1.028 2-OCH₃, 4-CI 5-CI H H

1.029 2-OCH₃, 4-CI 4-CI H H

1.030 2-OCH₃, 4-CI 4-Br H H

1.031 2-CH₃, 4-CH₂CN H H 4-NHCOCH₃

1.032 2-CH₃, 4-CI 4-CH₂CN H H

1.033 2-CH₃, 4-F 4-CH₂CN H H

1.034 2-OCH_3> 4-CH(CH₃)CN H H 4-CH=NOCH₃

Comp. Ri R₂ R3 R₄ Phys. Data

No. m.p. (°C)

1.062 2-OCH₃, 4-CF₃ 4-CN H H

1.063 2-OCH₃, 4-CI 5-Br H H

1.064 2-OCH₃₎ 4-F 5-Br H H

1.065 2-F, 4-CI 5-Br H H

1.066 2-F, 4-CI 4-CH(CH₃)CN H H

1.067 2-F, 4-CI 4-CH(CH₃)CN CH₃ H

1.068 2-F, 4-CI 4-CH(CH₃)CN CH₃ CH₃

1.069 2-OCHs, 4-CI 4-CH(CH₃)CN CHs H

1.070 2-OCHs, 4-CI 4-CH(CH₃)CN CH₃ CHs

1.071 2-OCH₃, 4-F 4-CH(CH₃)CN CH₃ H

1.072 2-OCH₃, 4-F 4-CH(CH₃)CN CHs CH₃

1.073 2-OCH₃, 4-CI 4-C(CH₃)₂CN H H

1.074 2-OCH₃, 4-F 4-C(CH₃)₂CN H H

1.075 2-CF₃ 4-CH₂CN H H

1.076 2-CFs, 4-CI 4-CH₂CN H H

1.077 2-CFs, 4-F 4-CH₂CN H H

1.078 2-OCHs, 4-CI 4-CH₂C(S)NH₂ H H

1.079 • 2-OCHs, 4-F 4-CH₂C(S)NH₂ H H

1.080 2-F, 4-CI 4-CH₂C(S)NH₂ H H

1.081 2-OCHs, 4-F 5-CHO H H solid

1.082 2-OCH₃, 4-CI 3-CONH₂ H H

1.083 2-OCHs, 4-CI 5-CO₂CH₃ H H

1.084 2-OCH3, 4-CI 3-F, 4-F, 5-F H H

1.085 4-CH₂CN 5-CH₃ H H MS: [M+H]⁺

1.086 2-OCH₃,6- 5-CH₃ H H MS: [M+H]⁺ OCH₃, 4-CH₂CN

1.087 2-OCH₃, 4-CI 3-OCF₃, 5-Br H H

1.088 2-OCH3, 4-CI 5-F H H

1.089 2-OCHs, 4-CI 3-F, 5-F H H

1.090 2-OCH3 5-CH3 H H MS: [M+H]⁺

1.091 2-OCH₃, 4-CI 3-F, 5-CI H H

1.092 2-OCH₃, 4-CI 5-CF3 H H

Comp. Rt R₂ Ra R₄ Phys. Data

No. m.p. (°C)

1.152 2-F, 4-CI 4-Br H H

1.153 2-CI, 4-CI 4-Br H H

1.154 2-F, 4-F 4-Br H H

1.155 2-OCHs, 4-Br 4-Br H H

1.156 2-F, 4-CI 4-OSO₂CH₃ H H

1.157 2-F, 4-F 4-OSO₂CH₃ H H

1.158 2-CI, 4-CI 4-OSO₂CH₃ H H

1.159 2-OCH3, 4-CI 4-OSO₂CH₃ H H

1.160 2-OCH₃, 4-Br 4-OSO₂CH₃ H H

1.161 2-OCH₃, 4-F 4-OSO₂CH₃ H H

1.162 2-OCH₃₎ 4-OSO₂CH₃ H H 4-CH=NOCH₃

1.163 2-OCH3, 4-Br 4-CI H H

1.164 2-OCH₃, 4-CF₃ 4-CI H H

1.165 2-F, 4-CI 4-CI H H

1.166 2-F, 4-F 4-CI H H

1.167 2-OCH₃, 4-F 4-OCH3 H H

1.168 2-F, 4-CI 4-OCH3 H H

1.169 2-CI, 4-CI 4-OCH₃ H H

1.170 2-OCH₃, 4-Br 4-OCH₃ H H

1.171 2-F, 4-F 4-OCH₃ H H

1.172 2-OCH₃, 4-CI 4-OCH₃ H H

1.173 2-F, 4-F 4-CH(CH₃)CN H H

1.174 2-OCH₃, 4-CF₃ 4-CH(CH₃)CN H H

1.175 2-OCH₃, 4-CN 4-Br H H

1.176 2-OCH₃, 4-CN 4-OSO₂CH₃ H H

1.177 2-OCH₃, 4-CN 4-CI H H

1.178 2-OCH₃, 4-CN 4-OCH3 H H

1.179 2-OCHs, 4-CN 4-I H H

1.180 2-F, 4-CI 4-I H H

1.181 2-CI, 4-CI 4-I H H

1.182 2-OCH_3l 4-F 4-I H H Comp. Rt R₂ R₃ R₄ Phys. Data

No. m.p. (°C)

1.183 2-OCH₃, 4-CI 4-I H H

1.184 2-OCH₃, 4-Br 4-I H H

1.185 2-CF₃, 4-F 4-I H H

1.186 2-OCH₃, 4-CF₃ 4-I H H

1.187 2-F, 4-F 4-CH₂C(S)NH₂ H H

1.188 2-OCH₃, 4-CFs 4-CH₂C(S)NH₂ H H

1.189 2-CI, 4-CI 4-CH₂C(S)NH₂ H H

1.190 2-OCH3, 4-Br 4-CH₂C(S)NH₂ H H

1.191 2-OCH3, 4-CN 4-CH₂-CCH H H

1.192 2-F, 4-CI 4-CH₂-CCH H H

1.193 2-CI, 4-CI 4-CH₂-CCH H H

1.194 2-OCH3, 4-F 4-CH₂-CCH H H

1.195 2-OCHs, 4-CI 4-CH₂-CCH H H

1.196 2-OCH3, 4-Br 4-CH₂-CCH H H

1.197 2-CF₃, 4-F 4-CH₂-CCH H H

1.198 2-OCH3, 4-CFs 4-CH₂-CCH H H

1.199 2-OCH3, 4-CH₂-CCH H H 4-CH=NOCH₃

1.200 2-OCH3, 4-CN 4-CH₂-CH=CH₂ H H

1.201 2-F, 4-CI 4-CH₂-CH=CH₂ H H

1.202 2-CI, 4-CI 4-CH₂-CH=CH₂ H H

1.203 2-OCH3, 4-F 4-CH₂-CH=CH₂ H H

1.204 2-OCH₃, 4-CI 4-CH₂-CH=CH₂ H H

1.205 2-OCH3, 4-Br 4-CH₂-CH=CH₂ H H

1-206 2-CF_3l 4-F 4-CH₂-CH=CH₂ H H

1.207 2-OCHs, 4-CF₃ 4-CH₂-CH=CH₂ H H

1.208 2-OCH₃, 4-CH₃ 4-CH₂-CH=CH₂ H H

1.209 2-OCH₃, 4-CH₂-CH=CH₂ H H 4-CH=NOCH₃

1.210 2-CI, 4-CI 5-Br H H

1.211 2-OCH₃, 4-Br 5-Br H H

1.212 2-CF₃, 4-F 5-Br H H

Comp. i R₂ R₃ R₄ Phys. Data

No. m.p. (°C)

1.271 2-CI, 4-CI 4-CH(OCH₃)CN H H

1.272 2-OCH₃, 4-F 4-CH(OCH₃)CN H H

1.273 2-OCH₃, 4-CI 4-CH(OCH₃)CN H H

1.274 2-OCH₃, 4-Br 4-CH(OCH₃)CN H H

1.275 2-CF₃, 4-F 4-CH(OCH₃)CN H H

1.276 2-OCH₃, 4-CF₃ 4-CH(OCH₃)CN H H

1.277 2-OCH₃, 4-CH₃ 4-CH(OCH₃)CN H H

1.278 2-OCHs, 4-CH(OCH₃)CN H H 4-CH=NOCH₃

1.279 2-OCH₃, 4-CN 4-CH(OCH₃)₂ H H

1.280 2-F, 4-CI 4-CH(OCH₃)₂ H H

1.281 2-CI, 4-CI 4-CH(OCH₃)₂ H H

1.282 2-OCH₃, 4-F 4-CH(OCH₃)₂ H H

1.283 2-OCH₃, 4-CI 4-CH(OCH₃)₂ H H

1.284 2-OCH₃, 4-Br 4-CH(OCH₃)₂ H H

1.285 2-CF₃, 4-F 4-CH(OCH₃)₂ H H

1.286 2-OCH₃, 4-CF₃ 4-CH(OCH₃)₂ H H

1.287 2-OCH3, 4-CH3 4-CH(OCH₃)₂ H H

1.288 2-OCH₃, 4-CH(OCH₃)₂ H H 4-CH=NOCH₃

1.289 2-OCH3, 4-CN 4-CH₂Br H H

1.290 2-F, 4-CI 4-CH₂Br H H

1.291 2-CI, 4-CI 4-CH₂Br H H

1.292 2-OCH3, 4-F 4-CH₂Br H H

1.293 2-OCH3, 4-CI 4-CH₂Br H H

1.294 2-OCH3, 4-Br 4-CH₂Br H H

1.295 2-CF₃, 4-F 4-CH₂Br H H

1.296 2-OCH₃, 4-CF₃ 4-CH₂Br H H

1.297 2-OCH3, 4-CH₃ 4-CH₂Br H H

1.298 2-OCH₃, 4-CH₂Br H H 4-CH=NOCH₃

1.299 2-OCH3, 4-CN 4-CH₂CONH₂ H H Comp. Ri R₂ R₃ R Phys. Data

No. m.p. (°C)

1.300 2-F, 4-CI 4-CH₂CONH₂ H H

1.301 2-CI, 4-CI 4-CH₂CONH₂ H H

1.302 2-OCHs, 4-F 4-CH₂CONH₂ H H

1.303 2-OCHs, 4-CI 4-CH₂CONH₂ H H

1.304 2-OCH3, 4-Br 4-CH₂CONH₂ H H

1.305 2-CF₃, 4-F 4-CH₂CONH₂ H H

1.306 2-OCH3, 4-CF3 4-CH₂CONH₂ H H

1.307 2-OCH3, 4-CH3 4-CH₂CONH₂ H H

1.308 2-OCH3, 4-CH₂CONH₂ H H 4-CH=NOCH₃

1.309 2-F, 4-F 4-CH₂CN CH₃ CH₃

1.310 2-CI, 4-CI 4-CH₂CN CH₃ CH₃

1.311 2-OCH₃, 4-Br 4-CH₂CN CH₃ CH₃

1.312 2-OCH₃, 4-CH₃ 4-CH₂CN CH₃ CH₃

1.313 2-F, 4-F 4-CH₂CN (CH₂)₂

1.314 2-F, 4-CI 4-CH₂CN (CH₂)₂

1.315 2-OCH₃, 4-F 4-CH₂CN (CH₂)₂

1.316 2-OCH₃, 4-CI 4-CH₂CN (CH₂)₂

1.317 2-F, 4-F 4-CH₂CN (CH₂)₄

1.318 2-F, 4-CI 4-CH₂CN (CH₂)₄

1.319 2-OCH3, 4-F 4-CH₂CN (CH₂)₄

1.320 2-OCH3, 4-CI 4-CH₂CN (CH₂)₄

1.321 2-F, 4-F 4-CH(CH₃)CN (CH₂)₂

1.322 2-F, 4-CI 4-CH(CH₃)CN (CH₂)₂

1.323 2-OCH3, 4-F 4-CH(CH₃)CN (CH₂)₂

1.324 2-OCH3, 4-CN 4-CH=NOCH₃ H H

1.325 2-F, 4-CI 4-CH=NOCH₃ H H

1.326 2-CI, 4-CI 4-CH=NOCH₃ H H

1.327 2-OCH3, 4-F 4-CH=NOCH₃ H H

1.328 2-OCH₃, 4-CI 4-CH=NOCH₃ H H

1.329 2-OCH₃, 4-Br 4-CH=NOCH₃ H H

1.330 2-CF3, 4-F 4-CH=NOCH₃ H H

Comp. Rt R₂ R₃ R₄ Phys. Data

No. m.p. (°C)

2.088 2-CH₃, 4-F 5-CH₂CN H H

2.089 2-CH₃, 4-CI 5-CH₂CN H H

2.090 2-OCHs, 4-Br 5-CH₂CN H H

2.091 2-OCH₃, 4-CH3 5-CH₂CN H H

2.092 2-OCH3, 4-CN 5-CH₂C(S)NH₂ H H

2.093 2-OCHs, 4-CI 5-CH₂C(S)NH₂ H H

2.094 2-OCH3, 4-F 5-CH₂C(S)NH₂ H H

2.095 2-OCH3 5-CH₂C(S)NH₂ H H

2.096 2-OCH3, 4- 5-CH(CN)CH₃ H H CH=NOCH₃

2.097 2-OCH₂F, 4-CI 5-CH(CN)CH₃ H H

2.098 2-OCH₂F, 4-F 5-CH(CN)CH₃ H H

2.099 2-OCH3, 4-Br 5-CH(CN)CH₃ H H

2.100 2-OCH3, 4-CF3 4-F, H H 5-CH(CN)CH₃

2.101 2-OCH3, 4-F 4-F, H H 5-CH(CN)CH₃

2.102 2-OCH3, 4-CI 4-F, H H 5-CH(CN)CH₃

Biological Examples

Example B1 : Herbicidal action prior to emergence of the plants (pre-emergence action) Monocotyledonous and dicotyledonous test plants are sown in standard soil in pots. Immediately after sowing, the test compounds, in the form of an aqueous suspension (prepared from a wettable powder (Example F3, b) according to WO 97/34485) or in the form of an emulsion (prepared from an emulsifiable concentrate (Example F1 , c) according to WO 97/34485), are applied by spraying in an optimum concentration (500 litres of water/ha). The test plants are then grown in a greenhouse under optimum conditions. After a test duration of 4 weeks, the test is evaluated in accordance with a scale of ten ratings (10 = total damage, 0 = no action). Ratings of from 10 to 7 (especially from 10 to 8) indicate good to very good herbicidal action. The test compounds show good results.

The same results are obtained when the compounds of formula I are formulated in accordance with the other Examples analogously to WO 97/34485.

Example B2: Post-emergence herbicidal action

Monocotyledonous and dicotyledonous test plants are sown in standard soil in pots. When the test plants are at the 2- to 3-leaf stage, the test compounds, in the form of an aqueous suspension (prepared from a wettable powder (Example F3, b) according to WO 97/34485) or in the form of an emulsion (prepared from an emulsifiable concentrate (Example F1 , c) according to WO 97/34485), are applied by spraying in an optimum concentration (500 litres of water/ha). The test plants are then grown on in a greenhouse under optimum conditions. After a test duration of 2 to 3 weeks, the test is evaluated in accordance with a scale of ten ratings (10 = total damage, 0 = no action). Ratings of from 10 to 7 (especially from 10 to 8) indicate good to very good herbicidal action.

Test plants: Echinochloa, Brachiaria, Scirpus

In the above Table, " - " indicates that no data are available.

The same results are obtained when the compounds of formula I are formulated in accordance with the other Examples analogously to WO 97/34485.

Claims

What is claimed is:

1. A compound of formula

wherein n is O, 1 , 2, 3, 4 or 5; each Ri is independently halogen, -CN, -SCN, -SF_5l -NO₂, -NR₅R_6l -CO₂R₇, -CONR₈R₉,

-C(R₁₀)=NORn, -COR₁₂, -OR₁₃, -SR₁₄, -SOR₁₅, -SO₂R₁₆, -OSO₂R₁₇, d-Csalkyl, C₂-C₈alkenyl,

C₂-C₈alkynyl or C₃-C₆cycloalkyl; or CrC₈alkyl, C₂-C₈alkenyl or C₂-C₈alkynyl substituted from one to five times by halogen and/or once, twice or three times by -CN, -NO₂, -NR₁₈R₁₉, -

CO₂R₂₀, -CONR₂ιR₂₂, -COR₂₃, -C(R₂₄)=NOR₂₅, -C(S)NR₂₆R_27J -C(C C₄alkylthio)=NR₂₈, -

OR₂₉, -SR₃₀, -SOR₃₁, -SO₂R₃₂ or C₃-C₆cycloalkyl; and/or each R is C₃-C₆cycloalkyl substituted from one to five times by halogen and/or once, twice or three times by -CN, -NO₂, -NR₁₈R₁₉, -CO₂R₂₀, -CONR₂₁R₂₂, -COR₂₃, -C(R₂₄)=NOR₂₅,

-C(S)NR₂₆R₂₇, -C(C C₄alkylthio)=NR₂₈, -SR₃₀, -SOR₃₁, -SO₂R₃₂ or C₃-C₆cycloalkyl; and/or each R_T is independently phenyl, which may itself be substituted from one to five times by halogen and/or once, twice or three times by Cj-C₄alkyl, d-C₄haloalkyl, d-C₄alkoxy, -CN,

-NO₂₎ C C₄alkylthio, C C₄alkylsulfinyl or d-C alkylsulfonyl; and/or two adjacent R together form a C C₇alkylene bridge, which may be interrupted by 1 or 2 non-adjacent oxygen atoms and substituted by d-Cβalkyl, the total number of ring atoms being at least 5 and at most 9; and/or two adjacent R^ together form a C₂-C₇alkenylene bridge, which may be interrupted by 1 or 2 non-adjacent oxygen atoms and substituted by Cι-C₆alkyl, the total number of ring atoms being at least 5 and at most 9;

R₃ and R₄ are each independently of the other hydrogen, halogen, -CN, d-C₄alkyl or C C - alkoxy; or

R₃ and R₄ together are C₂-C₅alkylene;

R₅ is hydrogen or C C₈alkyl;

R₆ is hydrogen, Cι-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by d-C₄alkyl, d-C₄haloalkyl, d-C₄alkoxy, -CN, -NO₂, C C₄alkylthio, d-C₄alkylsulfinyl or Cι-C₄alkylsulfonyl; or

R₅ and R₆ together are a C₂-C₅alkylene chain, which may be interrupted by an oxygen atom or a sulfur atom;

R₇ is hydrogen, C C₈alkyl, C₃-C₈alkenyl or C₃-C₈alkynyl, or d-C₈alkyl, C₃-C₈alkenyl or

C₃-C₈alkynyl substituted from one to five times by halogen or once, twice or three times by d-C₄alkoxy or phenyl, wherein phenyl may itself be substituted from one to five times by halogen and/or once, twice or three times by d-C₄alkyl, d-C₄haloalkyl, d-C₄alkoxy, -CN,

-NO₂, d-C₄alkylthio, C C₄alkylsulfinyl or d-C₄alkylsulfonyl;

R₈ is hydrogen or d-C₈alkyl;

R₉ is hydrogen or C C₈alkyl, or d-C₈alkyl substituted once, twice or three times by COOH, d-C₈alkoxycarbonyl or -CN; or

R₉ is C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by C C₄alkyl, d-C₄haloalkyl, C C₄alkoxy, -CN, -NO₂, d-C₄alkylthio, C C₄alkylsulfinyl or C C₄alkylsulfonyl; or

R₈ and R₉ together are C₂-C₅alkylene;

R₁₀ is hydrogen, d-C₄alkyl, d-C₄haloalkyl or C₃-C₆cycloalkyl;

Ru is hydrogen, C C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, Cι-C₄haloalkyl or C₃-C₆haloalkenyl;

R₁₂ is hydrogen, d-C₄alkyl, d-C₄haloalkyl or C₃-C₆cycloalkyl;

R₁₃ is hydrogen, Cι-C₈alkyl, C₃-C₈alkenyl or C₃-C₈alkynyl; or

R₁₃ is phenyl or phenyl-d-C₆alkyl, wherein the phenyl rings may themselves be substituted from one to five times by halogen and/or once, twice or three times by C C₄alkyl, d-C₄halo- alkyl, C C₄alkoxy, -CN, -NO₂ or -S(O)₂C C₈alkyI; or

R₁₃ is Cι-C₈alkyl substituted from one to five times by halogen or once, twice or three times by -CN or d-C₄alkoxy;

R₁₄ is hydrogen, d-C₈alkyl, C₃-C₈alkenyl or C₃-C₈alkynyl, or d-C₈alkyI substituted from one to five times by halogen or once, twice or three times by -CN or C_rC alkoxy;

R₁5, R₁₆ and R₁₇ are each independently of the others Cι-C₈alkyl, C₃-C₈alkenyl or C₃-C₈- alkynyl, or d-C₈alkyl substituted from one to five times by halogen or once, twice or three times by -CN or Cι-C₄alkoxy;

R₁₈ is hydrogen or C C₈alkyl;

R₁₉ is hydrogen, d-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by d-C₄alkyl, C C₄ha!oalkyl, C C alkoxy, -CN, -NO₂, C C₄alkylthio, C C₄- alkylsulfinyl or d-C alkylsulfonyl; or R ₈ and R₁₉ together are a C₂-C₅alkylene chain, which may be interrupted by an oxygen atom or a sulfur atom;

R₂₀ is hydrogen, d-Csalkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by d-C₄alkyl, C C₄haloalkyl, C C₄alkoxy, -CN, -NO₂, d-C₄alkylthio, C C₄- alkylsulfinyl or d-C₄alkylsulfonyl;

R₂₁ is hydrogen or d-C₈alkyl;

R₂₂ is hydrogen or d-C₈alkyl, or Cι-C₈alkyl substituted once, twice or three times by COOH,

Cι-C₈alkoxycarbonyl or -CN, or

R₂₂ is C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by C C₄alkyl, C C₄haloalkyl, C C₄alkoxy, -CN, -NO₂, d-C₄alkylthio, C C₄alkylsulfinyl or d-C alkylsulfonyl; or

R₂ι and R₂₂ together are C₂-C₅alkylene;

R₂₃ is hydrogen, d-C₄alkyl, CrC₄haloalkyl or C₃-C₆cycloalkyl;

R₂₄ is hydrogen, d-C₄alkyl, d-C₄haloalkyI or C₃-C₆cycloalkyl;

R₂₅ is hydrogen, d-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, C C₄haloalkyl or C₃-C₆haloalkenyl;

R₂₆ is hydrogen or Cι-C₈alkyl;

R₂₇ is hydrogen or d-C₈alkyl, or d-C₈alkyl substituted once, twice or three times by COOH, d-C₈alkoxycarbonyl or -CN; or

R₂₇ is C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by C C₄alkyl, C C₄haloalkyl, C C₄alkoxy, -CN, -NO₂, d-C₄alkylthio, C C₄alkylsulfinyl or Cι-C₄alkylsulfonyI; or

R₂₆ and R₂₇ together are C₂-C₅alkylene;

R₂₈ is hydrogen or d-C₈alkyl;

R₂₉ and R₃₀ are each independently of the other hydrogen, Cι-C₈alkyl, C₃-C₈alkenyl or C₃-C₈- alkynyl, or d-C₈alkyl substituted from one to five times by halogen or once, twice or three times by -CN or C C₄alkoxy;

R₃₁ and R₃₂ are each independently of the other d-C₈alkyl, C₃-C₈alkenyl or C₃-C₈alkynyl, or d-C₈alkyl substituted from one to five times by halogen or once, twice or three times by -CN or d-C₄alkoxy; m is 0, 1 , 2 or 3; each R₂ is independently halogen, -CN, -SCN, -SF₅, -NO₂, -NR₃₆R₃₇, -CO₂R₃₈, -CONR₃₉R₄₀,

-C(R₄₁)=NOR₄₂, -COR^, -ORw, -SR₄₅, -SOR₄₆, -SO₂R_47l -OSO₂R ₈, -N([CO]_PR₄₉)COR₅₀,

-N(OR₅₁)COR₅₂, -N(R₅3)CO₂R54 or -N-phthalimide; R₃₆ is hydrogen or d-C₈alkyl; and

R₃₇ is hydrogen, d-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by d-C₄alkyl, d-C₄haloalkyl, d-C₄alkoxy, -CN, -NO₂, C C₄alkylthio, C_rC₄- alkylsulfinyl or Cι-C₄alkylsulfonyl; or

R₃₆ and R₃₇ together are a C -C₅alkylene chain, which may be interrupted by an oxygen atom or a sulfur atom;

R₃₈ is hydrogen, d-C₈alkyl, C₃-C₈alkenyl or C₃-C₈alkynyl, or d-C₈alkyl, C₃-C₈alkenyl or

C₃-C₈alkynyl substituted from one to five times by halogen or once, twice or three times by d-C₄alkoxy or phenyl, wherein phenyl may itself be substituted from one to five times by halogen and/or once, twice or three times by d-C alkyl, d-C₄haloalkyl, d-C alkoxy, -CN,

-NO₂, d-C alkylthio, d-C alkylsulfinyl or d-C₄alkylsulfonyl;

R₃₉ is hydrogen or d-C₈alkyl;

R ₀ is hydrogen or Cι-C₈alkyl, or d-C₈alkyl substituted once, twice or three times by -COOH, d-C₈alkoxycarbonyl or -CN; or

R ₀ is C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by d-C₄alkyl, d-C₄haloalkyl, C C₄alkoxy, -CN, -NO₂, C C₄alkylthio, Cι-C₄alkylsulfinyl or Cι-C₄alkylsulfonyl; or

R₃₉ and R₄₀ together are C₃-C₅alkylene;

R ₁ is hydrogen, d-C alkyl, d-C₄haloalkyl or C₃-C₆cycloalkyl;

R ₂ is hydrogen, d-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, d-C₄haloalkyl or C₃-C₆haloalkenyl;

R₄₃ is hydrogen, d-C₄alkyl, C C₄haloalkyl or C₃-C₆cycloalkyl;

R is hydrogen, d-C₈alkyl, C₃-C₈alkenyl or C₃-C₈alkynyl; or

R is phenyl or phenyl-d-C₆alkyl, wherein the phenyl rings may themselves be substituted from one to five times by halogen and/or once, twice or three times by Cι-C alkyl, Cι-C₄halo- alkyl, d-C₄alkoxy, -CN, -NO₂ or -S(O)₂C_rC₈alkyl, or

R₄₄ is d-C₈alkyl substituted from one to five times by halogen or once, twice or three times by-CN or d-C₄alkoxy;

R^ is hydrogen, Cι-C₈alkyl, C₃-C₈alkenyl or C₃-C₈alkynyl, or C C₈alkyl substituted from one to five times by halogen or once, twice or three times by -CN or Cι-C₄alkoxy;

R₄₆, R₄₇ and R₄₈ are each independently of the others d-C₈alkyl, C₃-C₈alkenyl or C₃-C₈- alkynyl, or d-C₈alkyl substituted from one to five times by halogen or once, twice or three times by -CN or Cι-C alkoxy; p is 0 or 1 ; R₄₉, R₅₀, R₅₁, R₅₂, R₅3 and R₅ are each independently of the others hydrogen, d-C₈alkyl or phenyl, which may itself be substituted from one to five times by halogen and/or once, twice or three times by d-C₈alkyl, d-C₄haloalkyl, C C₄alkoxy, -CN, -NO₂, C C₈alkylthio, d-C₈- alkylsulfinyl or C C₈alkylsulfonyl; and/or each R₂ is independently d-C₈alkyl, or d-C₈alkyl substituted from one to five times by halogen or once, twice or three times by -CN, -NO₂, -NR5₅R56, -CO₂R₅₇, -CONR₅₈R₅₉,

-COR₆o, -C(R₆₁)=NOR₆₂, -C(S)NR₆₃R₆₄, -C(C_rC₄alkylthio)=NR₆₅, -OR₆₆, -SR₆₇, -SOR₆₈,

-SO₂R₆₉, -O(SO₂)R₇₀, -N(R₇₁)CO₂R₇₂, -N(R₇₃)COR₇₄ or C₃-C₆cycloalkyl; and/or each R₂ is independently C₂-C₈alkenyl, or C₂-C₈alkenyl substituted from one to five times by halogen or once, twice or three times by -CN, -NO₂, -CO₂R₇₅, -CONR₇₆R₇₇, -COR₇₈,

-C(R₇₉)=NOR₈₀, -C(S)NR₈₁R₈₂, -C(C C₄alkylthio)=NR₈₃ or C₃-C₆cycloalkyl; and/or each R₂ is independently C₂-C₈alkynyl, or C₂-C₈alkynyl substituted from one to five times by halogen or once, twice or three times by -CN, -CO₂R₈₄, -CONR₈₅R₈₆, -COR₈₇, -

C(R₈₈)=NOR₈₉, -C(S)NR₉₀R₉₁, -C(d-C₄alkylthio)=NR₉₂ or C₃-C₆cycloalkyl; and/or each R₂ is independently C₃-C₆cycloalkyl, or C₃-C₆cycloalkyl substituted from one to five times by halogen or once, twice or three times by -CN, -CO₂R₉₃, -CONR₉₄R₉₅, -COR₉₆,

-C(R₉₇)=NOR₉₈, -C(S)NR₉₉R₁₀o or -C(d-C₄alkyIthio)=NR₁₀ι; and/or two adjacent R₂ together form a C C₇alkylene bridge, which may be interrupted by 1 or 2 non-adjacent oxygen atoms and substituted by d-C₆alkyl, the total number of ring atoms being at least 5 and at most 9; and/or two adjacent R₂ together form a C₂-C₇alkenylene bridge, which may be interrupted by 1 or 2 non-adjacent oxygen atoms and substituted by d-C₆alkyl, the total number of ring atoms being at least 5 and at most 9;

R₅₅ is hydrogen or d-C₈alkyl;

R₅₆ is hydrogen, C C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by d-C₄alkyl, C C₄haloalkyl, CrC alkoxy, -CN, -NO₂, C C₄alkylthio, d-C₄- alkylsulfinyl or d-C alkylsulfonyl; or

R₅₅ and R₅₆ together are a C₂-C₅alkylene chain, which may be interrupted by an oxygen atom or a sulfur atom;

R₅₇ is hydrogen, C C₈alkyl, C₃-C₈alkenyl or C₃-C₈alkynyl, or d-C₈alkyl, C₃-C₈alkenyl or

C₃-C₈alkynyl substituted from one to five times by halogen or once, twice or three times by

C C₄alkoxy or phenyl, wherein phenyl may itself be substituted from one to five times by halogen and/or once, twice or three times by Cι-C₄alkyl, d-C₄haloalkyl, d-C₄alkoxy, -CN,

-NO₂, d-dalkylthio, Cι-C₄alkylsulfinyl or d-C₄alkylsulfonyl;

R₅₈ is hydrogen or d-C₈alkyl; R₅₉ is hydrogen or d-C₈alkyl, or d-C₈alkyl substituted once, twice or three times by -COOH, d-C₈alkoxycarbonyl or -CN; or

R₅₉ is C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by C C₄alkyl, C C₄haloalkyl, C C₄alkoxy, -CN, -NO₂, C C₄alkylthio, C C₄alkylsulfinyl or d-C₄alkylsulfonyl; or

R₅₈ and R₅₉ together are C₂-C₅alkylene;

R₆₀ is hydrogen, C C₄alkyl, C C₄haloalkyl or C₃-C₆cycloalkyl;

R₆₁ is hydrogen, C C₄alkyl, C C₄haloalkyl or C₃-C₆cycloalkyl;

R₆₂ is hydrogen, C C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, d-C₄haloalkyl or C₃-C₆haloalkenyl; and

R₆₃ is hydrogen or d-C₈alkyl;

R₆₄ is hydrogen or Cι-C₈alkyl, or d-C₈a)kyl substituted once, twice or three times by -COOH, d-Csalkoxycarbonyl or -CN; or

R₆₄ is C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by C C₄alkyl, d-C₄haloalkyl, d-C₄alkoxy, -CN, -NO₂, C C₄alkylthio, C C₄alkylsulfinyl or C C₄alkyIsulfonyl; or

R₆₃ and R^ together are C₂-C₅alkylene;

R₆₅ is hydrogen or d-C₈alkyl;

R₆₆ and R₆₇ are each independently of the other hydrogen, C C₈alkyl, C₃-C₈alkenyl or

C₃-C₈alkynyl, or Cι-C₈alkyl substituted from one to five times by halogen or once, twice or three times by -CN or C C₄alkoxy;

R₆₈ R₆₉ and R₇₀ are each independently of the others C C₈alkyl, C₃-C₈alkenyl or C₃-C₈- alkynyl, or d-C₈alkyl substituted from one to five times by halogen or once, twice or three times by -CN or C C₄alkoxy;

R₇₁ and R₇₃ are each independently of the other hydrogen, d-C₈alkyl or d-C₈alkoxy;

R₇₂ is C C₈alkyl;

R₇₄ is hydrogen or d-C₈alkyl;

R₇₅ is hydrogen, or C C₈alkyl, C₃-C₈alkenyl or C₃-C₈alkynyl each of which may be substituted from one to five times by halogen or once, twice or three times by Cι-C₄alkoxy or phenyl, wherein phenyl may itself be substituted from one to five times by halogen and/or once, twice or three times by d-C alkyl, Cι-C₄haloalkyl, d-C₄alkoxy, -CN, -NO₂, Cι-C₄alkyl- thio, Cι-C₄alkylsulfinyl or C C₄alkylsulfonyl;

R₇₆ is hydrogen or C C₈alkyl; R₇₇ is hydrogen or C C₈alkyl, or d-C₈alkyl substituted once, twice or three times by -COOH,

C -C₈alkoxycarbonyl or -CN; or

R₇₇ is C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by C C₄alkyl, C C₄haloalkyl, C C₄alkoxy, -CN, -NO₂₎ Cι-C₄alkylthio, d-C₄alkylsulfinyl or C C₄alkylsulfonyl; or

R₇₆ and R₇₇ together are C₂-C₅alkylene;

R₇₈ and R₇₉ are each independently of the other hydrogen, d-C₄alkyl, d-C₄haloalkyl or

C₃-C₆cycloalkyl;

R₈₀ is hydrogen, d-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, C C₄haloalkyl or C₃-C₆haloalkenyI;

R₈ι is hydrogen or d-C₈alkyl;

R₈₂ is hydrogen or CrC₈alkyl, or d-C₈alkyl substituted once, twice or three times by -COOH,

Cι-C₈alkoxycarbonyl or -CN; or

R₈₂ is C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by C C₄alkyl, C C₄haloalkyl, C C₄alkoxy, -CN, -NO₂, d-C₄alkylthio, d-C₄alkylsulfinyl or d-C₄alkylsulfonyl; or

R₈ι and R₈₂ together are C₂-C₅alkylene;

R₈₃ is hydrogen or CrCsalkyl;

R₈₄ is hydrogen, or Cι-C₈alkyl, C₃-C₈alkenyl or C₃-C₈alkynyl each of which may be substituted from one to five times by halogen or once, twice or three times by Cι-C₄alkoxy or phenyl, wherein phenyl may itself be substituted from one to five times by halogen and/or once, twice or three times by C C₄alkyl, d-C haloalkyl, d-C₄alkoxy, -CN, -NO₂, C_rC₄alkyl- thio, d-C alkylsulfinyl or d-C alkylsulfonyl;

R₈₅ is hydrogen or d-C₈alkyl;

R₈₆ is hydrogen or C C₈alkyl, or d-C₈alkyl substituted once, twice or three times by -COOH,

Cι-C₈alkoxycarbonyl or -CN; or

R₈₆ is C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by C C₄alkyl, d-C₄haloalkyl, d-C₄alkoxy, -CN, -NO₂, Cι-C₄alkylthio, C C₄aIkylsulfinyl or d-C₄alkylsulfonyl; or

R₈₅ and R₈₆ together are C₂-C₅alkylene;

R₈₇ is hydrogen, d-C₄alkyl, C C₄haloalkyl or C₃-C₆cycloalkyl;

R₈₈ is hydrogen, Cι-C₄alkyl, C C₄haloalkyl or C₃-C₆cycloalkyl;

R₈₉ is hydrogen, d-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, C C₄haloalkyl or C₃-C₆haloalkenyl;

R₉₀ is hydrogen or d-C₈alkyI; R₉₁ is hydrogen or d-C₈alkyl, or d-C₈alkyl substituted once, twice or three times by -COOH, d-C₈alkoxycarbonyl or -CN; or

R₉₁ is C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by C C₄alkyl, C₁-C haloalkyl, d-C₄alkoxy, -CN, -NO₂, C C₄alkylthio, C C₄alkylsulfinyl or d-C₄alkylsulfonyl; or

Rgo and R₉₁ together are C₂-C₅alkylene;

R₉₂ is hydrogen or d-C₈alkyl;

R₉₃ is hydrogen, or Cι-C₈alkyl, C₃-C₈alkenyl or C₃-C₈alkynyl each of which may be substituted from one to five times by halogen or once, twice or three times by Cι-C₄alkoxy or phenyl, wherein phenyl may itself be substituted from one to five times by halogen and/or once, twice or three times by d-C alkyl, CrC₄haloalkyl, d-C alkoxy, -CN, -NO₂, d-C₄alkyl- thio, d-C₄alkylsulfinyl or Cι-C₄alkylsulfonyl;

R₉₄ is hydrogen or d-C₈alkyl;

R₉₅ is hydrogen or Cι-C₈alkyl, or Cι-C₈alkyl substituted once, twice or three times by -COOH,

Cι-C₈alkoxycarbonyl or -CN; or

R₉₅ is C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by C C₄alkyl, d-C₄haloalkyl, d-C₄alkoxy, -CN, -NO₂, C C₄alkylthio, d-C₄alkylsulfinyl or d-C₄alkylsulfonyl; or

R₉₄ and R₉₅ together are C₂-C₅alkylene;

R₉₆ is hydrogen, CrC₄alkyl, C C₄haloalkyl or C₃-C₆cycloalkyl;

R₉₇ is hydrogen, C C₄alkyl, C C haloalkyl or C₃-C₆cycloalkyl;

R₉₈ is hydrogen, d-C₈alkyl, C₃-C₈alkenyl, C₃-C₈alkynyl, Cι-C haloalkyl or C₃-C₆haloalkenyl;

R₉₉ is hydrogen or Cι-C₈alkyl;

R₁₀₀ is hydrogen or d-C₈alkyl, or C C₈alkyl substituted once, twice or three times by

-COOH, C C₈alkoxycarbonyl or -CN; or

R₁₀₀ is C₃-C₈alkenyl, C₃-C₈alkynyl, phenyl or benzyl, wherein phenyl and benzyl may themselves be substituted from one to five times by halogen and/or once, twice or three times by C C₄alkyl, C₁-C₄haloalkyl, C C₄alkoxy, -CN, -NO₂, d-dalkylthio, C C₄alkylsulfinyl or C C alkylsulfonyl; or

R₉₉ and R₁₀₀ together are C₂-C₅alkylene; and

R₁₀ι is hydrogen or d-C₈alkyl, or an agrochemically acceptable salt or any stereoisomer or tautomer of a compound of formula I.

2. A process for the preparation of a compound of formula I according to claim 1 , which comprises reacting a compound of formula II

wherein R^ and n are as defined for formula I, in the presence of a base, with a compound of formula III

wherein R₃ and R₄ are as defined for formula I and X^ is O-tosyl, -OH, chlorine, bromine or iodine, to form a compound of formula IV

wherein Ri, R₃, R₄ and n are as defined for formula I, and then coupling that compound with a compound of formula V

wherein R₂ and m are as defined for formula I and A is a leaving group, in the presence of a palladium catalyst.

3. A herbicidal and plant-growth-inhibiting composition comprising a herbicidally effective amount of a compound of formula I with an inert carrier.

4. A method of controlling undesired plant growth, which method comprises applying a compound of formula l, or a composition comprising such a compound, in a herbicidally effective amount to plants or to the locus thereof.

5. A method of inhibiting plant growth, which method comprises applying a compound of formula I, or a composition comprising such a compound, in a herbicidally effective amount to plants or to the locus thereof.

6. A compound according to claim 1 , wherein each Ri is independently halogen, -CN, -NO₂, -C(R₁₀)=NOR₁₁, -ORιs, -SO₂R₁₆, -OSO₂R₁₇, C C₈alkyl or C₂-C₈alkenyl, and/or C C₈alkyl substituted from one to five times by halogen and/or once, twice or three times by -CN;

Rio is hydrogen or Cι-C₄alkyl; Ru is d-C₈alkyl; and R₁3 is C C₄alkyl.

7. A compound according to claim 1 , wherein each R₂ is independently halogen, -CN, -NO₂, -NR₃₆R37, -CO₂R₃8, -C(R₄ι)=NOR₄₂, -OR*,,

-SO₂R₄₇, -OSO₂R ₈or CrC₈alkyl, and/or C C₈alkyl substituted from one to five times by halogen and/or once, twice or three times by -CN or -CO₂R₅₇;

R₃₆ and R₃₇ are hydrogen;

R₃₈ is hydrogen or CrC₈alkyl;

R₄ι is hydrogen or d-C₄alkyl; and

R₄₂ is Cι-C₈alkyl.

8. A compound according to claim 1 , wherein each Ri is independently halogen, -CN, -NO₂, -C(R₁₀)=NORn, -OR₁₃, -SO₂Rι₆, -OSO₂Rι₇, C C₈alkyl or C₂-C₈alkenyl, and/or C C₈alkyl substituted once, twice or three times by -CN;

R-io is hydrogen or d-C₄alkyl;

Ru is CrC₈alkyl; and

R₁₃ is d-dalkyl; each R₂ is independently halogen, -CN, -NO₂, -NR₃₆R₃7, -CO₂R₃₈, -C(R₄₁)=NOR₄₂, -OR^,

-SO₂R₄₇, -OSO₂R₄₈ or Cι-C₈alkyl, and/or d-C₈alkyl substituted once, twice or three times by

-CN or -CO₂R₅₇;

R₃₆ and R₃₇ are hydrogen;

R₃₈ is hydrogen or Cι-C₈alkyl;

R ι is hydrogen or d-C₄alkyl;

R₄₂ is d-C₈alkyl; and

R₃ and R₄ are each independently of the other hydrogen or Cι-C₄alkyl.

9. A compound according to claim 1, wherein each R is independently halogen or-CN, and/or C C₈alkyl substituted by -CN, and/or C C₈alkoxy.

10. A compound according to claim 1, wherein each R₂ is independently halogen or-CN, and/or C C₈alkyl substituted by -CN, and/or C C₈alkoxy.