The invention relates to novel substituted N-aryl nitrogen-containing heterocyclic compounds of the general formula (I)

The invention relates to novel substituted N-aryl nitrogen-containing heterocyclic compounds, processes for their preparation and their use as herbicides.
It is known that certain N-aryl nitrogen-containing heterocyclic compounds have herbicidal properties (cf. EP 11693, DE 2952685, DE 3026739, U.S. Pat. Nos. 4,276,420, 4,326,878, WO 94/14817). However, the compounds known from the patent applications mentioned have not acquired noteworthy importance.
The novel substituted N-aryl nitrogen-containing heterocyclic compounds of the general formula (I)
in which
Q1 represents oxygen or sulfur,
Q2 represents oxygen or sulfur,
R1 represents hydrogen, cyano or formyl or represents alkyl which is optionally substituted by halogen, cyano, carboxyl, alkoxy, alkenyloxy, alkinyloxy, alkylthio, alkenylthio, alkinylthio, alkoxycarbonyl, alkenyloxycarbonyl or alkinyloxycarbonyl,
R1 furthermore represents alkenyl or alkinyl, in each case optionally substituted by halogen,
R1 furthermore represents alkylcarbonyl, alkenylcarbonyl, alkinylcarbonyl, alkoxycarbonyl, alkenyloxycarbonyl or alkinyloxycarbonyl, in each case optionally substituted by halogen,
R1 furthermore represents cycloalkyl or cycloalkylcarbonyl, in each case optionally substituted by halogen, cyano or carboxyl,
R2 represents hydrogen, cyano or formyl, or represents alkyl which is optionally substituted by halogen, cyano, carboxyl, alkoxy, alkenyloxy, alkinyloxy, alkylthio, alkenylthio, alkinylthio, alkoxycarbonyl, alkenyloxycarbonyl or alkinyloxycarbonyl,
R2 furthermore represents alkenyl or alkinyl, in each case optionally substituted by halogen,
R2 furthermore represents alkylcarbonyl, alkenylcarbonyl, alkinylcarbonyl, alkoxycarbonyl, alkenyloxycarbonyl or alkinyloxycarbonyl, in each case optionally substituted by halogen,
R2 furthermore represents cycloalkyl or cycloalkylcarbonyl, in each case optionally substituted by halogen, cyano or carboxyl, and
Ar represents the substituted monocyclic or bicyclic aryl or heteroaryl grouping defined below.
in which
R3 represents hydrogen or halogen,
R4 represents hydrogen or halogen,
R5 represents cyano, carboxyl, chlorocarbonyl, carbamoyl, thiocarbamoyl, hydroxyl or halogen, or represents alkyl, alkoxy or alkoxycarbonyl, in each case optionally substituted by halogen,
R6 represents the following grouping
xe2x80x94A1xe2x80x94A2xe2x80x94A3
xe2x80x83in which
A1 represents a single bond, or represents oxygen, sulfur, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94 or the grouping xe2x80x94Nxe2x80x94A4xe2x80x94, in which A4 represents hydrogen, hydroxyl, alkyl, alkenyl, alkinyl, alkoxy, aryl, alkylcarbonyl, arylcarbonyl, alkylsulfonyl or arylsulfonyl,
A1 furthermore represents alkanediyl, alkenediyl, azaalkenediyl, alkinediyl, cycloalkanediyl, cycloalkenediyl or phenylene, in each case optionally substituted by halogen,
A2 represents a single bond, or represents oxygen, sulfur, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94 or the grouping xe2x80x94Nxe2x80x94A4xe2x80x94, in which A4 represents hydrogen, hydroxyl, alkyl, alkoxy, aryl, alkylsulfonyl or arylsulfonyl,
A2 furthermore represents alkanediyl, alkenediyl, azaalkenediyl, alkinediyl, cycloalkanediyl, cycloalkenediyl or phenylene, in each case optionally substituted by halogen,
A3 represents hydrogen, with the proviso that in this case A1 and/or A2 do(es) not represent any single bond,
A3 furthermore represents hydroxyl, mercapto, amino, cyano, isocyano, thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulfo, chlorosulfonyl or halogen, or represents alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino, alkoxycarbonyl or dialkoxy-(thio) phosphoryl, in each case optionally substituted by halogen or alkoxy,
A3 furthermore represents alkenyl alkenyloxy, alkenylthio, alkenylamino, alkylidenamino, alkenyloxycarbonyl, alkinyl, alkinyloxy, alkinylthio, alkinylamino or alkinyloxycarbonyl, in each case optionally substituted by halogen,
A3 furthermore represents cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylidenamino, cycloalkyloxycarbonyl or cycloalkylalkoxycarbonyl, in each case optionally substituted by halogen, cyano, carboxyl, alkyl and/or alkoxy-carbonyl,
A3 furthermore represents aryl, aryloxy, aralkyl, arylalkoxy, aryloxycarbonyl or arylalkoxycarbonyl, in each case optionally substituted by nitro, cyano, carboxyl, halogen, alkyl, halogenalkyl, alkyloxy, halogenalkyloxy and/or alkoxy-carbonyl,
A3 furthermore represents m each case optionally completely or partly hydrogenated pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, oxiranyl, oxetanyl, dioxolanyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylalkyl, furylalkyl, thienylalkyl, oxazolylalkyl, isoxazolylalkyl, thiazolylalkyl, pyridinylalkyl, pyrimidinylalkyl, pyrazolylalkoxy or furylalkoxy, or represents perhydropyranylalkoxy or pyridylalkoxy, and
R7 represents hydrogen or halogen,
or in each case two adjacent radicals xe2x80x94R3 and R4, R4 and R5, R5 and R6 or R6 and R7xe2x80x94 together represent one of the following groupings
xe2x80x94Q3xe2x80x94CQ4xe2x80x94, xe2x80x94Q3xe2x80x94CQ4xe2x80x94Q5xe2x80x94, xe2x80x94Q3xe2x80x94C(R8,R9)xe2x80x94Q5xe2x80x94, xe2x80x94C(R8,R9)xe2x80x94CQ4xe2x80x94, xe2x80x94C(R8,R9)xe2x80x94Q3xe2x80x94CQ4xe2x80x94, xe2x80x94Q3xe2x80x94C(R8,R9)xe2x80x94C(R8,R9)xe2x80x94, xe2x80x94Q3xe2x80x94C(R8,R9)xe2x80x94C(R8,R9)xe2x80x94Q5xe2x80x94, xe2x80x94C(R8,R9)xe2x80x94C(R8,R9)xe2x80x94CQ4xe2x80x94, xe2x80x94Q3xe2x80x94C(R8)xe2x95x90C(R8)xe2x80x94, xe2x80x94C(R8)xe2x95x90C(R8)xe2x80x94CQ4xe2x80x94, xe2x80x94Q3xe2x80x94C(R8,R9)xe2x80x94CQ4xe2x80x94, xe2x80x94N(R10)xe2x80x94C(R8,R9)xe2x80x94CQ4xe2x80x94, xe2x80x94C(R8)xe2x95x90Nxe2x80x94, xe2x80x94Q3xe2x80x94CQ4xe2x80x94C(R8,R9)xe2x80x94, xe2x80x94Q3xe2x80x94CQ4xe2x80x94N(R10)xe2x80x94, xe2x80x94Q3xe2x80x94C(R8,R9)xe2x80x94CQ4xe2x80x94N(R10)xe2x80x94, xe2x80x94CR8, R9)xe2x80x94Q3xe2x80x94CQ4xe2x80x94N(R10)xe2x80x94, xe2x80x94C(R8,R9)xe2x80x94C(R8,R9)xe2x80x94N(R10)xe2x80x94, xe2x80x94C(R8,R9)xe2x80x94C(R8,R9)xe2x80x94CQ4xe2x80x94N(R10)xe2x80x94, xe2x80x94C(R8)xe2x95x90C(R8)xe2x80x94N(R10)xe2x80x94, xe2x80x94C(R8)xe2x95x90C(R8)xe2x80x94CQ4xe2x80x94N(R10)xe2x80x94, xe2x80x94C(R8,R9)xe2x80x94CQ4xe2x80x94N(R10)xe2x80x94, xe2x80x94N(R10)xe2x80x94C(R8,R9)xe2x80x94CQ4xe2x80x94N(R10)xe2x80x94, xe2x80x94C(R8)xe2x95x90Nxe2x80x94N(R10)xe2x80x94, xe2x80x94Q3Cxe2x80x94Q4xe2x80x94C(R8,R9)xe2x80x94N(R10)xe2x80x94, Q3xe2x80x94C(R8,R9)xe2x80x94(R8,R9)xe2x80x94CQ4xe2x80x94N(R10)xe2x80x94
in which
Q3, Q4 and Q5 are identical or different and in each case represent oxygen or sulfur,
R8 and R9 are identical or different and individually represent hydrogen, halogen or alkyl or together represent alkanediyl, and
R10 represents hydrogen or hydroxyl, or represents alkyl, alkylcarbonyl, alkoxycarbonyl or alkylsulfonyl which are optionally substituted by cyano, halogen, alkoxy, alkyl-carbonyl or alkoxy-carbonyl, or represents alkenyl or alkinyl, in each case optionally substituted by halogen, or represents cycloalkyl or cycloalkylalkyl, in each case optionally substituted by halogen or alkyl, or represents alkoxy or alkenyloxy, in each case optionally substituted by halogen, or represents arylalkyl or arylalkoxy, in each case optionally substituted by cyano, halogen, alkyl, halogenoalkyl, alkoxy or halogenoalkoxy,
have now been found, the already known compounds 4-(3,4-dichlorophenyl)-1,2-dimethyl-5-thioxo-1,2,4-triazolidin-3-one and 4-(4-chloro-3-trifluoromethylphenyl)-1,2-dimethyl-5-thioxo-1,2,4-triazolidin-3-one (cf. DE 2952685 and DE 3026739) being excluded by disclaimer.
The compounds isomeric to the substituted N-aryl nitrogen-containing heterocyclic compounds of the formula (I), of the formulae (Ia) and (Ib)
in which
Q1, Q2, R1, R2 and Ar have the abovementioned meanings, have furthermore also been found
The novel substituted N-aryl nitrogen-containing heterocyclic compounds of the general formula (I) and, where appropriate, the compounds of the formulae (Ia) or (Ib) are obtained when
(a) (thio)semicarbazide derivatives of the general formula (II)
in which
Q1, Q2, R1, R2 and Ar have the abovementioned meanings and
R represents alkyl,
are subjected to a cyclizing condensation reaction, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, and thereafter, if appropriate, electrophilic or nucleophilic substitution reactions are carried out in the customary manner in the context of the definition of the substituents,
or when
(b) aryliminoheterocyclic compounds of the general formula (III)
in which
Q1, Q2, R1, R2 and Ar have the abovementioned meanings, xe2x80x94or compounds of the formula (Ia) or (Ib)xe2x80x94abovexe2x80x94
are isomerized thermally (xe2x80x9cpyrolyticallyxe2x80x9d), if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent
The compounds of the formula (I) can in principle also be synthesized as shown schematically below:
(c) reaction of aryl iso(thio)cyanates of the formula (IV) with hydrazines of the formula (V) to give aryl(thio)semicarbazides of the formula (VI) and reaction thereof with (thio)phosgene:
(d) reaction of aryl iso(thio)cyanates of the formula (IV) with S-alkyldithiocarbazates of the formula (VII) and subsequent cyclizing condensation:
(e) reaction of N,N-bis-chlorocarbonyl- or N,N-bis-phenoxycarbonyl-arylamines of the formula (VIII)xe2x80x94Y:Cl or OC6H5xe2x80x94 with hydrazines of the formula (V):
(f) reaction of arylamines of the formula (IX) with hydrazinedicarboxylic acid esters of the formula (X):
The compounds of the general formula (I) can also be converted into other compounds of the general formula (I) according to the above definition by further customary methods, for example by customary conversions of carboxylic acid groupings or derivatives thereof (for example R5: COOHxe2x86x92COCl, COOHxe2x86x92COOCH3, COClxe2x86x92CONH2, COOCH3xe2x86x92CONH2, CONH2xe2x86x92CN, CNxe2x86x92CSNH2), by alkylation reactions (for example R1:Hxe2x86x92CH3 or CHF2) or by oxidation or sulfurization (for example Q1: Oxe2x86x92S or Sxe2x86x92O)xe2x80x94 cf. also the preparation examples.
The novel substituted N-aryl nitrogen-containing heterocyclic compounds of the general formula (I) are distinguished by a potent herbicidal activity.
In the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, alkenyl or alkinyl, are in each case straight-chain or branched.
Halogen in general represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.
The invention preferably relates to compounds of the formulae (I), (Ia) and (Ib) in which
Q1 represents oxygen or sulfur,
Q2 represents oxygen or sulfur,
R1 represents hydrogen, cyano or formyl, or represents C1-C6-alkyl, in each case optionally substituted by fluorine, chlorine, cyano, carboxyl, C1-C4-alkoxy, C3-C4-alkenyloxy, C3-C4-alkinyloxy, C1-C4-alkylthio, C3-C4-alkenylthio, C3-C4-alkinylthio, C1-C4-alkoxy-carbonyl, C3-C4-alkenyloxy-carbonyl or C3-C4-alki-nyloxy-carbonyl,
R1 furthermore represents C3-C6-alkenyl or C3-C6-alkinyl, in each case optionally substituted by fluorine or chlorine,
R1 furthermore represents C1-C6-alkyl-carbonyl, C3-C6-alkenyl-carbonyl, C3-C6-alkinyl-carbonyl, C1-C6-alkoxy-carbonyl, C1-C6-alkenyloxy-carbonyl or C3-C6-alkinyloxy-carbonyl, in each case optionally substituted by fluorine or chlorine,
R1 furthermore represents C3-C6-cycloalkyl or C3-C6-cycloalkyl-carbonyl, in each case optionally substituted by fluorine, chlorine, bromine, cyano or carboxyl,
R2 represents hydrogen, cyano or formyl, or represents C1-C6-alkyl, in each case optionally substituted by fluorine, chlorine, cyano, carboxyl, C1-C4-alkoxy, C3-C4-alkenyloxy, C3-C4-alkinyloxy, C1-C4-alkylthio, C3-C4-alkenylthio, C3-C4-alkinylthio, C1-C4-alkoxy-carbonyl, C3-C4-alkenyloxy-carbonyl or C3-C4-alki-nyloxy-carbonyl,
R2 furthermore represents C3-C6-alkenyl or C3-C6-alkenyl, in each case optionally substituted by fluorine or chlorine,
R2 furthermore represents C1-C6-alkyl-carbonyl, C3-C6-alkenyl-carbonyl, C3-C6-alkinyl-carbonyl, C1-C6-alkoxy-carbonyl, C3-C6-alkenyloxy-carbonyl or C3-C6-alkinyloxy-carbonyl, in each case optionally substituted by fluorine or chlorine,
R2 furthermore represents C3-C6-cycloalkyl or C3-C6-cycloalkyl-carbonyl, in each case optionally substituted by fluorine, chlorine, bromine, cyano or carboxyl, and
Ar represents the substituted monocyclic or bicyclic aryl or heteroaryl grouping defined below
in which
R3 represents hydrogen, fluorine, chlorine or bromine,
R4 represents hydrogen, fluorine, chlorine or bromine,
R5 represents cyano, carboxyl, chlorocarbonyl, carbamoyl, thiocarbamoyl, hydroxyl, fluorine, chlorine, bromine or represents alkyl, alkoxy or alkoxycarbonyl having in each case up to 4 carbon atoms and in each case optionally substituted by fluorine and/or chlorine,
R6 represents the following grouping
xe2x80x94A1xe2x80x94A2xe2x80x94A3
in which
A1 represents a single bond, or represents oxygen, sulfur, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94 or the grouping xe2x80x94Nxe2x80x94A4xe2x80x94, in which A4 represents hydrogen, hydroxyl, C1-C4-alkyl, C3-C4-alkenyl, C3-C4-alkinyl, C1-C4-alkoxy, phenyl, C1-C4-alkyl-carbonyl, phenylcarbonyl, C1-C4-alkyl-sulfonyl or phenylsulfonyl,
A1 furthermore represents C1-C6-alkanediyl, C2-C6-alkenediyl, C2-C6-azaalkenediyl, C2-C6-alkinediyl, C3-C6-cycloalkanediyl, C3-C6-cycloalkenediyl or phenylene, in each case optionally substituted by fluorine, chlorine or bromine,
A2 represents a single bond, or represents oxygen, sulfur, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94 or the grouping xe2x80x94Nxe2x80x94A4xe2x80x94, in which A4 represents hydrogen, hydroxyl, C1-C4-alkyl, C1-C4-alkoxy, phenyl, C1-C4-alkylsulfonyl or phenylsulfonyl,
A2 furthermore represents C1-C6-alkanediyl, C2-C6-alkenediyl, C2-C6-azaalkenediyl, C2-C6-alkinediyl, C3-C6-cycloalkanediyl, C3-C6-cycloalkenediyl or phenylene, in each case optionally substituted by fluorine, chlorine or bromine,
A3 represents hydrogen, with the proviso that in this case A1 and/or A2 do(es) not represent a single bond,
A3 furthermore represents hydroxyl, mercapto, amino, cyano, isocyano, thiocyanato, nitro, carboxyl, carbamoyl, thiocarbamoyl, sulfo, chlorosulfonyl, fluorine, chlorine or bromine,
A3 furthermore represents alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino, dialkylamino, alkoxycarbonyl or dialkoxy(thio)phosphoryl having in each case 1 to 6 carbon atoms in the alkyl groups and in each case optionally substituted by fluorine, chlorine or C1-C4-alkoxy,
A3 furthermore represents alkenyl, alkenyloxy, alkenylamino, alkylidenamino, alkenyloxycarbonyl, alkinyl, alkinyloxy, alkinylamino or alkinyloxycarbonyl having in each case 2 to 6 carbon atoms in the alkenyl, alkylidene or alkinyl groups and in each case optionally substituted by fluorine or chlorine,
A3 furthermore represents cycloalkyl, cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylidenamino, cycloalkyloxycarbonyl or cycloalkylalkoxycarbonyl having in each case 3 to 6 carbon atoms in the cycloalkyl groups and where appropriate 1 to 4 carbon atoms in the alkyl groups and in each case optionally substituted by fluorine, chlorine, cyano, carboxyl, C1-C4-alkyl and/or C1-C4-alkoxy-carbonyl,
A3 furthermore represents phenyl, phenyloxy, phenyl-C1-C4-alkyl, phenyl-C1-C4-alkoxy, phenyloxycarbonyl or phenyl-C1-C4-alkoxycarbonyl, in each case optionally substituted by nitro, cyano, carboxyl, fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-halogenalkyl, C1-C4-alkyloxy, C1-C4-halogenalkyloxy and/or C1-C4-alkoxy-carbonyl,
A3 furthermore represents in each case optionally completely or partly hydrogenated pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, oxiranyl, oxetanyl, dioxolanyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolyl-C1-C4-alkyl, furyl-C1-C4-alkyl, thienyl-C1-C4-alkyl, oxazolyl-C1-C4-alkyl, isoxazolyl-C1-C4-alkyl, thiazolyl-C1-C4-alkyl, pyridinyl-C1-C4-alkyl, pyrimidinyl-C1-C4-alkyl, pyrazolylmethoxy or furylmethoxy, or represents perhydropyranylmethoxy or pyridylmethoxy, and
R7 represents hydrogen, fluorine or chlorine,
or in each case two adjacent radicals xe2x80x94R3 and R4, R4 and R5, R5 and R6 or R6 and R7xe2x80x94 together represent one of the following groupings
xe2x80x94Q3xe2x80x94CQ4xe2x80x94, xe2x80x94Q3xe2x80x94CQ4xe2x80x94Q5xe2x80x94, xe2x80x94Q3xe2x80x94C(R8,R9)xe2x80x94Q5xe2x80x94, xe2x80x94C(R8,R9)xe2x80x94CQ4xe2x80x94, xe2x80x94C(R8,R9)xe2x80x94Q3xe2x80x94CQ4xe2x80x94, xe2x80x94Q3xe2x80x94C(R8,R9)xe2x80x94C(R8,R9)xe2x80x94, Q3xe2x80x94C(R8,R9)xe2x80x94C(R8,R9)xe2x80x94Q5xe2x80x94, xe2x80x94C(R8,R9)xe2x80x94C(R8,R9)xe2x80x94CQ4xe2x80x94, xe2x80x94Q3xe2x80x94C(R8)xe2x95x90C(R8)xe2x80x94, xe2x80x94C(R8)xe2x95x90C(R8)xe2x80x94CQ4xe2x80x94, xe2x80x94Q3xe2x80x94C(R8,R9)xe2x80x94CQ4xe2x80x94, xe2x80x94N(R10)xe2x80x94C(R8,R9)xe2x80x94, CQ4xe2x80x94, xe2x80x94C(R8)xe2x95x90Nxe2x80x94, xe2x80x94Q3xe2x80x94CQ4xe2x80x94C(R8,R9)xe2x80x94, xe2x80x94Q3xe2x80x94CQ4xe2x80x94(R10)xe2x80x94, xe2x80x94Q3xe2x80x94C(R8,R9)xe2x80x94CQ4xe2x80x94N(R10)xe2x80x94, xe2x80x94C(R8,R9)xe2x80x94Q3xe2x80x94CQ4xe2x80x94N(R10)xe2x80x94, xe2x80x94C(R8,R9)xe2x80x94C(R8, R9)xe2x80x94N(R10)xe2x80x94, xe2x80x94C(R8,R9)xe2x80x94C(R8,R9)xe2x80x94CQ4xe2x80x94N(R10)xe2x80x94, xe2x80x94C(R8)xe2x95x90C(R8)xe2x80x94N(R10)xe2x80x94, xe2x80x94C(R8)xe2x95x90C(R8)xe2x80x94CQ4xe2x80x94N(R10)xe2x80x94, xe2x80x94C(R8,R9)xe2x80x94CQ4xe2x80x94N(R10)xe2x80x94, N(R10)xe2x80x94C(R8,R9)xe2x80x94CQ4xe2x80x94N(R10)xe2x80x94, xe2x80x94C(R8)xe2x95x90Nxe2x80x94N(R10)xe2x80x94, xe2x80x94Q3xe2x80x94CQ4xe2x80x94C(R8,R9)xe2x80x94N(R10)xe2x80x94, xe2x80x94Q3xe2x80x94C(R8,R9)xe2x80x94C(R8,R9)xe2x80x94CQ4xe2x80x94N(R10)
in which
Q3, Q4 and Q5 are identical or different and in each case represent oxygen or sulfur,
R8 and R9 are identical or different and individually represent oxygen, fluorine, chlorine, bromine or C1-C4-alkyl or together represent C2-C5-alkanediyl, and
R10 represents hydrogen or hydroxyl, or represents alkyl, alkylcarbonyl, alkoxycarbonyl or alkylsulfonyl having in each case 1 to 6 carbon atoms in the alkyl groups and in each case optionally substituted by cyano, fluorine, chlorine, C1-C4-alkoxy, C1-C4-alkylcarbonyl or C1-C4-alkoxy-carbonyl,
R10 furthermore represents alkenyl or alkinyl having in each case 2 to 6 carbon atoms and in each case optionally substituted by fluorine, chlorine or bromine,
R10 furthermore represents cycloalkyl or cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl groups and where appropriate 1 to 3 atoms in the alkyl group and in each case optionally substituted by fluorine, chlorine, bromine or C1-C4-alkyl,
R10 furthermore represents alkoxy or alkenyloxy having in each case up to 6 carbon atoms and in each case optionally substituted by fluorine and/or chlorine, and
R10 furthermore represents benzyl or benzyloxy, in each case optionally substituted by cyano, fluorine, chlorine, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C4-alkoxy or C1-C4-halogenoalkoxy,
the already known compounds 4-(3,4-dichloro-phenyl)-1,2-dimethyl-5-thioxo-1,2,4-triazolidin-3-oneand4-(4-chloro-3-trifluoromethyl-phenyl)-1,2-dimethyl-5-thioxo-1,2,4-triazolidin-3-one (cf. DE 2952685 and DE 3026739) being excluded by disclaimer.
The invention particularly relates to compounds of the formulae (I), (Ia) and (Ib) in which
Q1 represents oxygen or sulfur,
Q2 represents oxygen or sulfur,
R1 represents hydrogen, cyano or formyl, or represents methyl, ethyl, n- or i-propyl or n-, i-, s- or t-butyl, in each case optionally substituted by fluorine, chlorine, cyano, carboxyl, methoxy or ethoxy,
R1 furthermore represents propenyl, butenyl, propinyl or butinyl, in each case optionally substituted by fluorine or chlorine,
R1 furthermore represents acetyl, propionyl, methoxycarbonyl or ethoxycarbonyl, in each case optionally substituted by fluorine or chlorine,
R1 furthermore represents cyclopropyl which is optionally substituted by fluorine or chlorine,
R2 represents hydrogen, cyano or formyl, or represents methyl, ethyl, n- or i-propyl or n-, i-, s- or t-butyl, in each case optionally substituted by fluorine, chlorine, cyano, carboxyl, methoxy or ethoxy,
R2 furthermore represents propenyl, butenyl, propinyl or butinyl, in each case optionally substituted by fluorine or chlorine,
R2 furthermore represents acetyl, propionyl, methoxycarbonyl or ethoxycarbonyl, in each case optionally substituted by fluorine or chlorine,
R2 furthermore represents cyclopropyl which is optionally substituted by fluorine or chlorine, and
Ar represents the substituted monocyclic or bicyclic aryl or heteroaryl grouping defined below
in which
R3 represents hydrogen, fluorine or chlorine,
R4 represents hydrogen, fluorine or chlorine,
R5 represents cyano, thiocarbamoyl, chlorine, bromine, methyl, trifluoromethyl, methoxy, difluoromethoxy or trifluoromethoxy,
R6 represents the following grouping
xe2x80x83xe2x80x94A1xe2x80x94A2xe2x80x94A3
in which
A1 represents a single bond, or represents oxygen, sulfur, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94 or the grouping xe2x80x94Nxe2x80x94A4xe2x80x94, in which A4 represents hydrogen, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulfonyl or ethylsulfonyl,
A1 furthermore represents methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2,-diyl, propene-1,2-diyl, propene-1,3-diyl, ethine-1,2-diyl, propine-1,2-diyl or propine-1,3-diyl,
A2 represents a single bond, or represents oxygen, sulfur, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94 or the grouping xe2x80x94Nxe2x80x94A4xe2x80x94, in which A4 represents oxygen, hydroxyl, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl or phenylsulfonyl,
A2 furthermore represents methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2-diyl, propene-1,2-diyl, propene-1,3-diyl, ethine-1,2-diyl, propine-1,2-diyl or propine-1,3-diyl,
A3 represents hydrogen, with the proviso that in this case A1 and/or A2 do(es) not represent a single bond,
A3 furthermore represents hydroxyl, amino, cyano, nitro, carboxyl, carbamoyl, sulfo, fluorine, chlorine or bromine,
A3 furthermore represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, n-, i-, s- or t-pentyloxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, dimethoxyphosphoryl, diethoxyphosphoryl, dipropoxyphosphoryl or diisopropoxyphosphoryl, in each case optionally substituted by fluorine, chlorine, methoxy or ethoxy,
A3 furthermore represents propenyl, butenyl, propenyloxy, butenyloxy, propenylamino, butenylamino, propylidenamino, butylidenamino, propenyloxycarbonyl, butenyloxycarbonyl, propinyl, butinyl, propinyloxy, butinyloxy, propinylamino, butinylamino, propinyloxycarbonyl or butinyloxycarbonyl, in each case optionally substituted by fluorine or chlorine,
A3 furthermore represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cylopentyloxy, cyclohexyloxy, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclo-butylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopentylidenamino, cyclohexylidenamino, cyclopentyloxy-carbonyl, cyclohexyloxycarbonyl, cyclopentylmethoxycarbonyl or cyclohexylmethoxycarbonyl, in each case optionally substituted by fluorine, chlorine, cyano, carboxyl, methyl, ethyl, n- or i-propyl, methoxycarbonyl or ethoxycarbonyl,
A3 furthermore represents phenyl, phenyloxy, benzyl, phenylethyl, benzyloxy, phenyloxycarbonyl or benzyloxycarbonyl, in each case optionally substituted by nitro, cyano, carboxyl, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methoxycarbonyl and/or ethoxycarbonyl,
A3 furthermore represents in each case optionally completely or partly hydrogenated pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylmethyl, furylmethyl, thienylmethyl, oxazolylmethyl, isoxazolylmethyl, thiazolylmethyl, pyridinylmethyl, pyrimidinylmethyl, pyrazolylmethoxy, furylmethoxy or pyridylmethoxy,
R7 represents hydrogen, fluorine or chlorine,
or in each case two adjacent radicalsxe2x80x94R3 and R4, R4 and R5, R5 and R6 or R6 and R7xe2x80x94together represent one of the following groupings
xe2x80x94Q3xe2x80x94CQ4xe2x80x94, xe2x80x94Q3xe2x80x94CQ4xe2x80x94Q5xe2x80x94, xe2x80x94Q3xe2x80x94C(R8,R9)xe2x80x94Q5xe2x80x94, xe2x80x94C(R8,R9)xe2x80x94CQ4xe2x80x94, xe2x80x94C(R8,R9)xe2x80x94Q3xe2x80x94CQ4xe2x80x94, xe2x80x94Q3xe2x80x94C(R8,R9)xe2x80x94C(R8,R9)xe2x80x94, xe2x80x94Q3xe2x80x94C(R8,R9)xe2x80x94C(R8,R9)xe2x80x94Q5xe2x80x94, xe2x80x94C(R8,R9)xe2x80x94C(R8,R9)xe2x80x94CQ4xe2x80x94, xe2x80x94Q3xe2x80x94C(R8)xe2x95x90C(R8)xe2x80x94, xe2x80x94C(R8)xe2x95x90C(R8)xe2x80x94CQ4xe2x80x94, xe2x80x94Q3C(R8,R9)xe2x80x94CQ4xe2x80x94, xe2x80x94N(R10)xe2x80x94C(R8,R9)xe2x80x94CQ4xe2x80x94, xe2x80x94C(R8)xe2x95x90Nxe2x80x94, xe2x80x94Q3xe2x80x94CQ4xe2x80x94C(R8,R9)xe2x80x94, xe2x80x94Q3xe2x80x94CQ4xe2x80x94N(R10)xe2x80x94, xe2x80x94Q3xe2x80x94C(R8,R9)xe2x80x94CQ4xe2x80x94N(R10)xe2x80x94, xe2x80x94C(R8,R9)xe2x80x94Q3xe2x80x94CQ4xe2x80x94N(R10)xe2x80x94, xe2x80x94C(R8,R9)xe2x80x94C(R8,R9)xe2x80x94N(R10)xe2x80x94, xe2x80x94C(R8,R9)xe2x80x94C(R8,R9)xe2x80x94CQ4xe2x80x94N(R10)xe2x80x94, xe2x80x94C(R8)xe2x95x90C(R8)xe2x80x94N(R10xe2x80x94, xe2x80x94C(R8)xe2x95x90C(R8)xe2x80x94CQ4xe2x80x94N(R10)xe2x80x94, xe2x80x94C(R8,R9)xe2x80x94CQ4xe2x80x94N(R10)xe2x80x94, xe2x80x94N(R10)xe2x80x94C(R8,R9)xe2x80x94CQ4xe2x80x94N(R10)xe2x80x94, xe2x80x94C(R8)xe2x95x90Nxe2x80x94N(R10)xe2x80x94, xe2x80x94Q3xe2x80x94CQ4xe2x80x94C(R8,R9)xe2x80x94N(R10)xe2x80x94, Q3xe2x80x94C(R8,R9)xe2x80x94C(R8,R9)xe2x80x94CQ4xe2x80x94N(R10)xe2x80x94,
in which
Q3, Q4 and Q5 are identical or different and in each case represent oxygen or sulfur,
R8 and R9 are identical or different and individually represent hydrogen, fluorine, chlorine, methyl or ethyl, or together represent ethane-1,2-diyl (dimethylene), and
R10 represents hydrogen or hydroxyl, or represents methyl, ethyl, n- or i-propyl or n-, i-, s- or t-butyl which are optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, acetyl, propionyl, methoxycarbonyl or ethoxycarbonyl,
R10 furthermore represents propenyl, butenyl, propinyl or butinyl, in each case optionally substituted by fluorine, chlorine or bromine,
R10 furthermore represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, in each case optionally substituted by fluorine, chlorine, bromine, methyl or ethyl,
R10 furthermore represents methoxy, ethoxy, n- or i-propoxy, n-, i- or s-butoxy, propenyloxy or butenyloxy, in each case optionally substituted by fluorine and/or chlorine, and
R10 furthermore represents benzyl or benzyloxy, in each case optionally substituted by cyano, fluorine, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethyl or trifluoromethoxy,
the already known compounds 4-(3,-dichloro-phenyl)-1,2-dimethyl-5-thioxo-1,2,4-triazolidin-3-oneand4-(4-chloro-3-trifluoromethyl-phenyl)-1,2-dimethyl-5-thioxo-1,2,4-triazolidin-3-one (cf. DE 2952685 and DE 3026739) being excluded by disclaimer.
The abovementioned definitions of radicals given generally or in preferred ranges apply both to the end products of the formula (I) and also correspondingly to the starting substances or intermediate products in each case required for the preparation. These definitions of radicals can be combined with one another as desired, that is to say also between the stated ranges of preferred compounds.
Examples of the compounds of the formula (I) according to the invention are given in the following groups.
Ar here has, for example, the meanings listed below:
2,4-dichloro-phenyl, 3-chloro-4-fluoro-phenyl, 2-chloro-4-cyano-phenyl, 2-fluoro-4-cyano-phenyl, 4,5-difluoro-phenyl, 2,4,5-trichloro-phenyl, 2,4-dichloro-5-fluoro-phenyl, 2-chloro-4,5-difluoro-phenyl, 4-chloro-2,5-di-fluoro-phenyl, 5-chloro-2,4-difluoro-phenyl, 2-fluoro-5-chloro-4-cyano-phenyl, 2,4,5-trifluoro-phenyl, 2,5-dichloro-4-cyano-phenyl, 2-chloro-5-fluoro-4-cyano-phenyl, 2-chloro-4,5-dicyano-phenyl, 2-chloro-4-fluoro-5-cyano-phenyl, 2,5-difluoro-4-cyano-phenyl, 4-cyano-3-methyl-phenyl, 2-chloro-4-cyano-5-methyl-phenyl, 2,4-dichloro-5-methoxy-phenyl, 2,4-dichloro-5-ethoxy-phenyl, 2,4-dichloro-5-n-propoxy-phenyl, 2,4-dichloro-5-i-propoxy-phenyl, 4-chloro-2-fluoro-5-methoxy-phenyl, 4-chloro-2-fluoro-5-ethoxy-phenyl, 4-chloro-2-fluoro-5-n-propoxy-phenyl, 4-chloro-2-fluoro-5-i-propoxy-phenyl, 2-fluoro-4-cyano-5-methyl-phenyl, 2,4-dichloro-5-methyl-phenyl, 2-chloro-4-cyano-5-trifluoromethyl-phenyl, 4-fluoro-3-trifluoromethyl-phenyl, 2-fluoro-4-cyano-5-trifluoromethyl-phenyl, 2-chloro-4-methyl-5-trifluoromethyl-phenyl, 2-chloro-5-fluoro-4-methoxy-phenyl, 2-fluoro-4-methoxy-5-methyl-phenyl, 2,5-difluoro-4-thicarbamoyl-phenyl, 2-chloro-4-fluoro-5-i-propoxy-phenyl, 2-fluoro-4-cyano-5-methoxy-phenyl, 2-fluoro-4-cyano-5-i-propoxy-phenyl, 2-chloro-4-cyano-5-(2-propinyloxy)-phenyl, 2-fluoro-4-cyano-5-(1-methyl-2-propinyloxy)-phenyl, 2-fluoro-4-chloro-5(1-methyl-2-propinyloxy)-phenyl, 2-chloro-4-thio-carbamoyl-5-i-propoxy-phenyl, 2-fluoro-4-cyano-5-(2-propenyloxy)-phenyl, 2-fluoro-4-chloro-5-(2-propenyloxy)-phenyl, 2-chloro-4-cyano-5-methyl-sulfonylamino-phenyl, 2-fluoro-4-cyano-5-ethylsulfonylamino-phenyl, 2-fluoro-4-thiocarbamoyl-5-methylsulfonylamino-phenyl, 2-chloro-4-cyano-5-ethylsulfonylamino-phenyl, 2-fluoro-4-cyano-5-cyclopropylsulfonylamino-phenyl, 2-fluoro-4-cyano-5-i-propylsulfonylamino-phenyl, 2-chloro-4-thiocarbamoyl-5-ethylsulfonylamino-phenyl, 2-chloro-4-cyano-5-cyanamino-phenyl, 2-fluoro-4-cyano-5-(2,2-difluoroethylsulfonylamino)-phenyl, 2-fluoro-4-cyano-5-phenyl-sulfonylamino-phenyl, 2-fluoro-4-cyano-5-t-butylsulfonyla-mino-phenyl, 2-chloro-4-cyano-5-methoxycarbonyl-phenyl, 2-fluoro-4-cyano-5-ethoxycarbonyl-phenyl, 2-fluoro-4-chloro-5-ethoxycarbonyl-phenyl, 2-fluoro-4-thiocarbamoyl-5-methoxy-carbonyl-phenyl, 2-chloro-4-cyano-5-(N-cyclopropyl-ethylsulfonylamino)-phenyl, 2-fluoro-4-cyano-5-(1-methyl-2-propinylthio)-phenyl, 2-fluoro-4-cyano-5-methylamino-phenyl, 2-chloro-4-thiocarbamoyl-5-methoxycarbonylmethyl-phenyl, 2-chloro-4-cyano-5-(N-methyl-ethylsulfonylamino)-phenyl, 2-fluoro-4-cyano-5-i-propoxycarbonyl-phenyl, 2-fluoro-4-chloro-5-i-propoxycarbonyl-phenyl, 2-fluoro-4-cyano-5-(bis-ethylsulfonyl-amino)-phenyl, 2-fluoro-4-cyano-5-(N-methylsulfonyl-ethylsulfonylamino)-phenyl, 2-fluoro-4-cyano-5(1-methoxycarbonyl-ethoxy)-phenyl, 2-fluoro-4-cyano-5(1-ethoxycarbonyl-ethoxy)-phenyl, 2-fluoro-4-chloro-5(1-methoxycarbonyl-ethoxy)-phenyl, 2-fluoro-4-chloro-5-(1-ethoxycarbonyl-ethoxy)-phenyl, 2-fluoro-4-cyano-5-cyclopropyloxy-phenyl, 2-chlooro-4-cyano-5-dimethylamino-phenyl, 2-fluoro-4-cyano-5-tetrahydrofurylmethoxy-phenyl, 4-chloro-2-fluoro-5-tetrahydrofurylmethoxy-phenyl, 2-fluoro-4-cyano-5-amino-phenyl, 2-fluoro-4-cyano-5-methylaminocarbonyl-phenyl, 2-fluoro-4-cyano-5-methylsulfonyloxy-phenyl, 2-chloro-4-cyano-5-difluoromethoxy-phenyl, 2-fluoro-4-chloro-5-methoxycarbonylmethoxy-phenyl, 2-fluoro-4-chloro-5-ethoxycarbonyl-methoxy-phenyl, 2-fluoro-4-cyano-5-methoxycarbonylmethoxy-phenyl, 2-fluoro-4-cyano-5-ethoxycarbonylmethoxy-phenyl, 4-cyano-3-(1-methyl-2-propinyloxy)-phenyl, 2-fluoro-4-cyano-5-dimethyl-aminocarbonyl-phenyl, 2-fluoro-4-cyano-5-cyanomethoxy-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-propenyloxy)-phenyl, 2-fluoro-4-cyano-5-hydroxy-phenyl, 2-fluoro-4-cyano-5-nitro-phenyl, 2-fluoro-4-cyano-5-diethoxyphosphorylamino-phenyl, 2-fluoro-4-cyano-5-chlorosulfonyl-phenyl, 2-fluoro-4-cyano-5-formylamino-phenyl, 2-chloro-4-cyano-5-ethoxycarbonyloxy-phenyl, 2-fluoro-4-cyano-5-diethoxyphosphorylmethoxy-phenyl, 4-chloro-2-fluoro-5-diethoxy-phosphorylmethoxy-phenyl, 2-fluoro-4-cyano-5-(1-diethoxyphosphoryl-ethoxy)-phenyl, 4-chloro-2-fluoro-5-(1-diethoxyphosphoryl-ethoxy)-phenyl-2-chloro-4-cyano-5-hydroxy-phenyl, 2-fluoro-4-cyano-5-(N,N-diacetyl-amino)-phenyl, 2-fluoro-4-cyano-5-acetylamino-phenyl, 2-chloro-4-cyano-5-thiocyanato-phenyl, 2-fluoro-4-cyano-5-diethylaminooxy-phenyl, 2-fluoro-4-cyano-5-tetrahydrofuryloxy-phenyl, 2-fluoro-4-cyano-5-ureido-phenyl, 2-fluoro-4-cyano-5-dimethoxymethylenamino-phenyl, 2-chloro-4-cyano-5-ethoxymethylenamino-phenyl, 2-fluoro-4-cyano-5-(2-chloro-ethoxycarbonyl-oxy)-phenyl, 2-chloro-4-cyano-5-dimethylaminomethylenamino-phenyl, 2-chloro-4-cyano-5-perhydropyran-4-yloxy)-phenyl, 2-fluoro-4-cyano-5-(2-methoxycarbonyl-ethyl)-phenyl, 4-chloro-2-fluoro-5-(2-methoxycarbonyl-ethyl)-phenyl, 2-chloro-4-cyano-5-(2-carboxy-2-chloro-ethyl)phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-methoxycarbonyl-ethyl)-phenyl, 2-fluoro-4-chloro-5-(2-chloro-2-methoxycarbonyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-ethoxycarbonyl-ethyl)-phenyl, 2-fluoro-4-chloro-5-(2-chloro-2-ethoxycarbonyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-bromo-2-methoxycarbonyl-ethyl)-phenyl, 2-fluoro-4-chloro-5-(2-bromo-2-methoxycarbonyl-ethyl)phenyl, 2-fluoro-4-cyano-5-(2-bromo-2-ethoxycarbonyl-ethyl)-phenyl, 2-fluoro-4-chloro-5-(2-bromo-2-ethoxycarbonyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2,3-dibromo-2-methoxycarbonyl-ethyl)-phenyl, 2-fluoro-4-chloro-5-(2,3-dibromo-2-methoxycarbonyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2,3-dibromo-2-ethoxycarbonyl-ethyl)-phenyl, 2-fluoro-4-chloro-5-(2,3-dibromo-2-ethoxycarbonyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-s-butoxycarbonyl)phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-carbamoyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-methoxycarbonyl-1-methyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(1,2-dibromo-2-methoxycarbonyl-ethyl)-phenyl, 2-chloro-4-cyano-5-(2-chloro-2-i-propoxy-carbonyl-ethyl)-phenyl, 2,4-dichloro-5-(2-methoxycarbonyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-carboxy-2-chloro-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-ethylamino-carbonyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-allylaminocarbonyl-2-chloro-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-methoxycarbonyl-ethenyl)-phenyl, 2-fluoro-4-chloro-5-(2-methoxycarbonyl-ethenyl)-phenyl, 2-fluoro-4-cyano-5-(2-ethoxycarbonyl-ethenyl)-phenyl, 2-fluoro-4-chloro-5-(2-ethoxycarbonyl-ethenyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-methylaminocarbonyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-ethylaminocarbonyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-cyclopropylamino-carbonyl-ethyl)-phenyl, 2-fluoro-4-chloro-5-(2-chloro-2-methylaminocarbonyl-ethyl)-phenyl, 2-fluoro-4-chloro-5-(2-chloro-2-ethylaminocarbonyl-ethyl)-phenyl, 2-fluoro-4-chloro-5-(2-chloro-2-cyclopropylaminocarbonyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-dimethylaminocarbonyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-ethylsulfonylaminocarbonyl-ethyl)-phenyl, 2-fluoro-4-chloro-5-(2-chloro-2-ethylsulfonylaminocarbonyl-ethyl)-phenyl, 2-fluoro-4-chloro-5-(2-carboxy-ethenyl)-phenyl, 2-fluoro-4-thiocarbamoyl-5-(2-ethylaminocarbonyl-ethenyl)-phenyl, 2,6-difluoro-4-cyano-5-i-propoxy-phenyl, 2-chloro-4-cyano-6-fluoro-3-i-propoxy-phenyl, 2-chloro-6-fluoro-3-i-propoxy-4-trifluoromethyl-phenyl, 2,6-di-chloro-4-cyano-3-fluoro-phenyl, 2-fluoro-4-cyano-5-(1-ethoxycarbonyl-ethyl)phenyl, 2-chloro-4-cyano-5-(1-ethoxycarbonyl-ethyl)-phenyl, 2-chloro-4-cyano-5-carboxy-phenyl, 2-fluoro-4-chloro-5-(1-ethoxycarbonyl-ethyl)-phenyl, 2-fluoro-4-chloro-5-(1-i-propoxycarbonyl-ethyl)-phenyl, 2-fluoro-4-cyano-5-i-butoxy-phenyl), 2-chloro-4-cyano-5-i-butoxy-phenyl, 2-chloro-4-cyano-5-(2-methoxy-ethoxy)-phenyl, 2-fluoro-4-chloro-5(2-methoxy-ethoxy)-phenyl, 2-fluoro-4-chloro-5-i-butoxy-phenyl, 4-hydroxy-4-ethoxycarbonyl-phenyl, 2-fluoro-4-cyano-5-i-propoxycarbonyl-phenyl, 2-fluoro-4-hydroxy-5-i-propoxycarbonyl-phenyl, 2-fluoro-4-cyano-5-(2-oxetanyloxy)-phenyl, 2-fluoro-4-cyano-5-(2-oxetanyloxy-carbonylmethoxy)-phenyl, 2-fluoro-4-cyano-5-(2-oxetanyloxy)-phenyl, 2-fluoro-4-cyano-5-(2-chloro-2-propenyloxy)-phenyl, 4-chloro-2-fluoro-5-(2-chloro-2-propenyloxy)-phenyl, 2-fluoro-4-chloro-5-methoxycarbonylmethylthio-phenyl, 2-fluoro-4-chloro-5-ethoxycarbonylmethylthio-phenyl, 2-fluoro-4-cyano-5-methoxycarbonylmethylthio-phenyl, 2-fluoro-4-cyano-5-ethoxycarbonylmethylthio-phenyl, 2-fluoro-4-chloro-5-(1-methoxycarbonyl-ethylthio)-phenyl, 2-fluoro-4-chloro-5(1-ethoxycarbonyl-ethylthio)-phenyl, 2-fluoro-4-cyano-5-(1-methoxycarbonyl-ethylthio)-phenyl, 2-fluoro-4-cyano-5-(1-ethoxycarbonyl-ethylthio)-phenyl,
R here represents, for example, hydrogen, hydroxyl, methyl, ethyl, n- or i-propyl, i- or s-butyl, allyl, propargyl, methoxy, ethoxy, n- or i-propoxy, cyanomethyl, carboxymethyl, methoxymethyl, ethoxymethyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylsulfonyl or ethylsulfonyl.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
Ar here has, for example, the meanings listed above in Group 1.
If, for example, 4(4-cyano-2,5-difluoro-phenyl)-1-methoxycarbonylthiosemicarbazide is used as the starting substance, the course of the reaction in process (a) according to the invention can be represented by the following equation:
If, for example, 2-(4-chloro-2-fluoro-5-methoxy-phenylimino)-3,4-dimethyl-3,4-dihydro-5-oxo-1,3,4-thiadiazole is used as the starting substance, the course of the reaction in process (b) according to the invention can be outlined by the following equation:
Formula (II) provides a general definition of the (thio)semicarbazide derivatives to be used as starting substances in process (a) according to the invention for the preparation of the compounds of the general formula (I). In formula (II), Q1, Q2, R1, R2 and Ar preferably or in particular have those meanings which have already been mentioned above as preferred or as particularly preferred for Q1, Q2, R1, R2 and Ar in connection with the description of the compounds of the formula (I); R preferably represents alkyl having 1-4 carbon atoms, in particular methyl or ethyl.
The starting substances of the formula (II) are known and/or can be prepared by known processes (cf. Synthesis 1982, 159-160; DE 1200824, DE 2952685 and DE 3026739).
The (thio)semicarbazide derivatives of the formula (II) are obtained when
(xcex1) aryl iso(thio)cyanates of the general formula (IV)
xe2x80x83Arxe2x80x94Nxe2x95x90Cxe2x95x90Q1xe2x80x83xe2x80x83(IV)
xe2x80x83in which
Ar and Q1 have the abovementioned meanings,
are reacted with carbazates of the general formula (XI)
ROxe2x80x94CQ2xe2x80x94N(R2)xe2x80x94NHxe2x80x94R1xe2x80x83xe2x80x83(XI)
xe2x80x83in which
Q2, R1 and R2 have the abovementioned meanings and
R represents alkyl, and preferably represents C1-C6-alkyl, and particularly preferably represents methyl or ethyl,
if appropriate in the presence of a diluent, such as, for example, toluene, at temperatures of between 0xc2x0 C. and 150xc2x0 C. (cf. the preparation examples),
or when
(xcex2) arylamines of the general formula (XII)
Arxe2x80x94NH2xe2x80x83xe2x80x83(XII)
xe2x80x83in which
Ar has the abovementioned meaning,
are reacted with (thio)carbonyl-diimidazole of the formula (XIII)
Imxe2x80x94CQ1xe2x80x94Imxe2x80x83xe2x80x83(XIII)
xe2x80x83in which
Q1 has the abovementioned meaning and
lm represents imidazolyl, and with carbazates of the general formula (XI)
ROxe2x80x94CQ2xe2x80x94N(R2)xe2x80x94NHxe2x80x94R1xe2x80x83xe2x80x83(XI)
xe2x80x83in which
Q2, R1 and R2 have the abovementioned meanings and
R represents alkyl, and preferably represents C1-C6-alkyl, and particularly preferably represents methyl or ethyl,
if appropriate in the presence of a reaction auxiliary, such as, for example, potassium hydroxide, and if appropriate in the presence of a diluent, such as, for example, methanol, ethanol and/or water, at temperatures of between 0xc2x0 C. and 100xc2x0 C.
The aryl iso(thio)cyanates of the formula (IV) required as precursors are known and/or can be prepared by known processes (cf. DE 4327743, DE 4335438 and DE 4343451).
The carbazates of the formula (VIII) furthermore required as precursors are known organic chemicals.
Process (a) according to the invention is preferably carried out in the presence of a suitable reaction auxiliary. Possible reaction auxiliaries are all the customary organic or inorganic bases. These include, for example, alkali metal or alkaline earth metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogencarbonates, such as, for example, lithium, sodium, potassium or calcium hydride, lithium, sodium or potassium amide, sodium or potassium methylate, sodium or potassium ethylate, sodium or potassium propylate, aluminum isopropylate, sodium or potassium tert-butylate, sodium or potassium hydroxide, ammonium hydroxide, sodium, potassium or calcium acetate, ammonium acetate, sodium, potassium, rubidium, cesium, magnesium or calcium carbonate, ammonium carbonate and sodium or potassium hydrogencarbonate, and basic organic nitrogen compounds, such as trimethylamine, triethylamine tripropylamine, tributylamine, ethyl-diisopropylamine, N,N-dimethylcyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N,N-dimethylaniline, N,N-dimethyl-benzylamine, pyridine, 2-methyl-, 3-methyl- and 4-methyl-pyridine, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, N-methylpiperidine, N,N-dimethylaminopyridine, diazabicyclooctane, (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).
Possible diluents for carrying out process (a) according to the invention are the customary organic solvents. These include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, pentane, hexane, heptane, petroleum ether, ligroin, benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, cyclohexane, methylcyclohexane, methylene chloride, chloroform or carbon tetrachloride; ethers, such as diethyl ether, diisopropyl ether, t-butyl methyl ether, t-pentyl methyl ether, dioxane, tetrahydro-furan, ethylene glycol dimethyl or diethyl ether or diethylene glycol dimethyl or diethyl ether; ketones, such as acetone, butanone or methyl isobutyl ketone; nitriles, such as acetonitrile, propionitrile, butyronitrile or benzonitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methyl-pyrrolidone or hexamethylphosphoric acid triamide; esters, such as methyl, ethyl, n- or i-propyl or n-, i- or s-butyl acetate; sulfoxides, such as dimethyl sulfoxide; alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, s- or t-butanol, ethylene glycol monomethyl or monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether; and mixtures thereof with water or pure water.
The reaction temperatures can be varied within a substantial range when carrying out process (a) according to the invention. The process is in general carried out at temperatures of between 0xc2x0 C. and +150xc2x0 C., preferably at temperatures between 10xc2x0 C. and 120xc2x0 C.
Process (a) according to the invention is in general carried out under normal pressure. However, it is also possible to carry out the process under increased or reduced pressurexe2x80x94in general between 0.1 bar and 10 bar.
For carrying out process (a) according to the invention, the starting substances of formula (II) are in general initially introduced into the reaction vessel in a suitable diluent andxe2x80x94if appropriate after addition of a reaction auxiliaryxe2x80x94are stirred at the required temperature until the reaction has ended. Working up can be carried out in the customary manner (cf. the preparation examples).
Formula (III) provides a general definition of the aryliminoheterocyclic compounds to be used as starting substances in process (b) according to the invention for the preparation of the compounds of the general formula (I). In formula (III), Q1, Q2, R1, R2 and Ar preferably or in particular have those meanings which have already been mentioned above as preferred or as particularly preferred for Q1, Q2, R1, R2 and Ar in connection with the description of the compounds of the formula (I).
The starting substances of the formula (III) are not yet known from the literature; however, they are the subject of a prior application which has not previously been published (cf. DE 4424787).
The aryliminoheterocyclic compounds of the formula (III) are obtained when aryl(thio)semicarbazides of the general formula (VI) are reacted with reactive carbonic acid derivatives, such as, for example, phosgene or thiophosgene, if appropriate in the presence of diluents, such as, for example, toluene and/or methylene chloride, at temperatures of between 0xc2x0 and 200xc2x0 C.
Formulae (Ia) and (Ib) provide general definitions of the compounds to be used, if appropriate, as starting substances, in process (b) according to the invention for the preparation of the compounds of the general formula (I). In formulae (Ia) and (Ib), Q1, Q2, R1, R2 and Ar preferably or in particular have those meanings which have already been mentioned above as preferred or as particularly preferred for Q1, Q2, R1, R2 and Ar in connection with the description of the compounds of the formula (I).
The compounds of the formula (Ia) or (Ib) are obtained when N-aryl nitrogen-containing heterocyclic compounds of the general formula (I) in which at least one of the groups R1 or R2 represents hydrogen are reacted with alkylating or acylating agents of the formulae (IXa or (IXb)
Xxe2x80x94R1xe2x80x83xe2x80x83(XIVa)
Xxe2x80x94R2xe2x80x83xe2x80x83(XIVb)
xe2x80x83in which
R1 and R2 have the abovementioned meanings, with the exception of hydrogen, and
X represents halogenxe2x80x94preferably chlorine, bromine or iodinexe2x80x94or one of the groupings xe2x80x94Oxe2x80x94SO2xe2x80x94R1 or xe2x80x94Oxe2x80x94SO2xe2x80x94R2,
if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary at temperatures of between 0xc2x0 C. and 80xc2x0 C. (cf. the preparation examples).
The same diluents and reaction auxiliaries as in process (a) according to the invention are preferably possible here.
If appropriate, process (b) according to the invention is carried out in the presence of a reaction auxiliary. The same reaction auxiliaries as in process (a) according to the invention, but furthermore in addition also alkali metal sulfides, such as, for example, sodium sulfide or potassium sulfide, are possible here.
Process (b) according to the invention is preferably carried out using a diluent. The same diluents as in process (a) according to the invention are possible here.
The reaction temperatures can be varied within a substantial range when carrying out process (b) according to the invention. The process is in general carried out at temperatures of between 0xc2x0 C. and +250xc2x0 C., preferably at temperatures of between 20xc2x0 C. and 150xc2x0 C.
Process (b) according to the invention is in general carried out under normal pressure. However, it is also possible to carry out the process under increased or reduced pressurexe2x80x94in general between 0.1 bar and 10 bar.
For carrying out process (b) according to the invention, the starting substances of the formula (III) or of the formulae (Ia) or (Ib)xe2x80x94are in general initially introduced into the reaction vessel in a suitable diluent and are stirred at the required temperature until the reaction has ended. Working up can be carried out in the customary manner.
The active compounds according to the invention can be used as defoliants, desiccants, agents for destroying broad-leaved plants and, especially, as weed-killers. By weeds, in the broadest sense, there are to be understood all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the following plants:
Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver Centaurea, Trifolium, Ranunculus, Taraxacum.
Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledon weeds of the genera: Echinchloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dartyloctenium, Agrostis, Alopecurus and Apera.
Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
The compounds are suitable, depending on the concentration, for the total combating of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for combating weeds in perennial cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, in lawns, turf and pasture-land, and for the selective combating of weeds in annual cultures.
The compounds of the formula (I) according to the invention are particularly suitable for selectively combating monocotyledon and dicotyledon weeds in monocotyledon cultures both by the pre-emergence and by the post-emergence method.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that is emulsifying agents and/or dispersing agents and/or foam-forming agents.
In the case of the use of water as an extender, organic solvents card for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, as well as water.
As solid carriers there are suitable: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, alumina and silicates, as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates as well as albumen hydrolysis products; as dispersing agents there are suitable: for example lignin-sulfite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Further additives can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
For controlling weeds, the active compounds according to the invention, as such or in the form of their formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
Suitable herbicides for the mixtures are known herbicides, for example anilides such as, for example, diflufenican and propanil; arylcarboxylic acids such as, for example, dichloropicolinic acid, dicamba and picloram; aryloxyalkanoic acids such as, for example, 2,4 D, 2,4 DB, 2,4 DP, fluroxypyr, MCPA, MCPP and triclopyr; aryloxy-phenoxy-alkanoic esters such as, for example, diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; azinones such as, for example, chloridazon and norflurazon; carbamates such as, for example, chlorpropham, desmedipham, phenmedipham and propham; chloroacetanilides such as, for example, alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor, dinitroanilines such as, for example, oryzalin, pendimethalin and trifluralin; diphenyl ethers such as, for example, acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; ureas such as, for example, chlortoluron, diuron, fluometuron, isoproturon, linuron and methabenzthiazuron; hydroxylamines such as, for example, alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim; imidazolinones such as, for example, imazethapyr, imazamethabenz imazapyr and imazaquin; nitriles such as, for example, bromoxynil, dichlobenil and ioxynil; oxyacetamides such as, for example, mefenacet; sulfonylureas such as, for example, amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl and tribenuron-methyl; thiocarbamates such as, for example, butylate, cycloate, di-allate, EPTC, esprocarb, molinate, prosulfocarb, thiobencarb and tri-allate; triazines such as, for example, atrazine, cyanazine, simazine, simetryne, terbutryne and terbutylazine; triazinones such as, for example, hexazinone, metamitron and metribuzin; others such as, for example, aminotriazole, benfuresate, bentazone, cinmethylin, clomazone, clopyralid, difenzo-quat, dithiopyr, ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac, sulphosate and tridiphane.
A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents for improving soil structure is also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing or scattering.
The active compounds according to the invention can be applied either before or after emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha
The preparation and use of the active compounds according to the invention can be seen from the following examples.

Substituted N-aryl nitrogen-containing heterocyclic compounds

Abstract: and to the compounds isomeric to the substituted N-aryl nitrogen-containing heterocyclic compounds of the formula (I), of the formulae (Ia) and (Ib)

Abstract: in which

Abstract: Q1, Q2, R1, R2 and Ar have the meanings given in the description, processes for their preparation and their use as herbicides.


A sample vial [24] is disclosed, having a generally tubular body [32]. The vial [24] has a generally round lip [34] defining an opening [36] at the top of the body [32]. The vial [24] has a foot [38] at the base of the body [32], having asymmetric first and second sides [40, 42]. A rack [28] is disclosed for supporting such a sample vial [24]. The rack [28] supports the sample vial [24] in a generally upright position in a single orientation. The rack [28] has an asymmetric recess [50] adapted to receive the asymmetric foot [38] in a single orientation. The rack [28] also has an orientation abutment [82] adapted to interfere with a projecting abutment [46] of a vial [24] to prevent insertion of a vial [24] into the asymmetric recess [50] in an orientation other than the single orientation. The orientation abutment [82] also allows insertion of a vial [24] into the asymmetric recess [50] in the single orientation.

Sample vials are used for collecting multiple specimens of analytes for analysis. For example, on a dairy farm, the milk of each animal may be sampled frequently and the samples sent to a laboratory to analyze them for fat content, impurities, any indications of disease, or other properties. The sample vials are then often discarded, so a large demand exists for inexpensive sample vials.
Certain sample vials commonly used for collecting milk specimens have previously been generally tubular with a round cross-section from bottom to top, a flat or concave bottom allowing the vials to stand up on a flat, level surface, and an integral lid joined to the body by an integral hinge. The sample vials have been carried in racks, resembling a common test tube rack, having wells that each receive a vial but do not latch the vial in place.
One piece liquid-tight vials are discussed in U.S. Pat. Nos. 4,783,056; 4,812,116; RE 37,676; and 6,303,064.


A phase interpolator includes an adaptively biased phase mixer, phase control circuitry and an adaptive bias generator. The adaptively biased phase mixer has mixing transistor circuitry configured to provide an output phase signal in response to a plurality of phase control signals, a bias current, and a number of phase input signals offset in phase from one another. The adaptively biased phase mixer further has adjustable bias transistor circuitry configured to adjust the bias current provided to the mixing transistor circuitry in response to an adaptive bias signal.

Phase interpolators are circuits that are used in many types of electronic systems, such as, for example, clock-data recovery systems. A phase interpolator receives as inputs a phase selection signal and two or more phase input signals having the same frequency as each other but offset in phase from each other. In response to these inputs, the phase interpolator produces a phase output signal having a phase specified by the phase selection signal. The phase interpolator produces the phase output signal by mixing two of the phase input signals in a ratio derived from the phase selection signal.
As illustrated in FIG. 1, a known phase interpolator 10 includes an adaptive bias generator 12, a triangle wave generator (TWG) 14, a fixed-bias phase mixer 16, phase control logic 18, and a logic level converter 20. Triangle wave generator 14 receives as inputs four phase input (clock) signals, each of which is offset from another by 90 degrees. For example, the four phase input signals can have phases relative to one another of zero degrees (PH0), 90 degrees (PH90), 180 degrees (PH180) and 270 degrees (PH270). Triangle wave generator 14 processes or conditions each of these four phase input signals by buffering the signal, and then using the buffered signal to control the charging and discharging of capacitor circuits (not separately shown). Triangle wave generator 14 includes one such capacitor circuit for each of the four phase input signals. Triangle wave generator 14 limits the current with which each of its four capacitor circuits is charged, such that the capacitor circuit charges for one-half clock cycle and discharges for one-half clock cycle.
As illustrated in FIG. 2, adaptive bias generator 12 in effect functions as a frequency-dependent current source that controls the bias current (I_BIAS_ADAPTIVE) with which triangle wave generator 14 charges each of its capacitors. The purpose of adaptive bias generator 12 is to compensate for (or "adapt" to) variations in mixer operating conditions, such as system clock frequency, supply voltage, etc. Adaptive bias generator 12 includes a comparator 22, a current source 24, two switches 26 and 28, a capacitor 30, and switch control logic 32. Switch control logic 32 controls switches 26 and 28 in response to the system clock. During the first half clock cycle of the system clock, switch control logic 32 closes switch 26 to charge capacitor 30 to a voltage Vsum while maintaining switch 28 open. During the second half clock cycle of the system clock, switch control logic 32 opens switch 26 and closes switch 28 to discharge capacitor 30 to ground. The combination of switches 26 and 28 and capacitor 30 is commonly referred to as a switched-capacitance resistor circuit 34. The feedback loop involving comparator 22 and current source 24 operates to ensure that the bias current (I_BIAS_ADAPTIVE) is sufficient to maintain Vsum equal to a reference voltage (V_REF) and thus to keep the bias current directly proportional to the frequency of the system clock. Thus, adaptive bias generator 12 directly adapts to or compensates for variations in system clock frequency and indirectly adapts to or compensates for voltage and temperature variations. Although not shown for purposes of clarity, current mirrors can be included to replicate the bias current for distribution to all four of the above-referenced capacitor circuits of triangle wave generator 14.
For example, in an instance in which the system clock signal has a frequency that is twice a frequency f, adaptive bias generator 12 generates a bias current that is twice the bias current that it generates when the system clock signal frequency is f. Using adaptive bias generator 12 to control the bias current with which triangle wave generator 14 charges each of its capacitors promotes a linear response to the system clock signal frequency. (Although not shown for purposes of clarity, it should be noted that the four phase input signals are generated from the system clock signal and therefore have the same frequency as the system clock signal.) Accordingly, triangle wave generator 14 generates four corresponding triangle-wave signals in response to the four square-wave phase input signals. The output of triangle wave generator 14 thus consists of four triangle-wave phase output signals having relative phases of zero degrees, 90 degrees, 180 degrees and 270 degrees.
Returning to FIG. 1, phase control logic 18 receives a phase selection signal as an input. The phase selection signal indicates a selected phase in a range greater than or equal to 0 degrees and less than 360 degrees. Phase control logic 18 determines which two of the four phase input signals the selected phase lies between and determines a ratio indicating the relative distances of the selected phase between those two phase input signals. For example, if the phase selection signal indicates a selected phase of 120 degrees, phase control logic 18 determines that the selected phase lies between the 90-degree phase input signal (PH90) and the 180-degree phase input signal (PH180) and determines that the selected phase of 120 degrees lies one-third of the distance (i.e., 90 degrees) from the 90-degree phase input signal to the 180-degree phase input signal, and correspondingly, two-thirds of the distance from the 180-degree phase input signal to the 90-degree phase input signal.
As illustrated in FIG. 3, fixed-bias phase mixer 16 includes a first buffer 36, a second buffer 38, a third buffer 40, and a fourth buffer 42. The input of first buffer 36 receives the 0-degree phase input signal, and the output of first buffer 36 is connected to a common node that serves as the output of fixed-bias phase mixer 16 (PH_OUT). The input of second buffer 38 receives the 90-degree phase input signal, and the output of second buffer 38 is connected to this common node. The input of third buffer 40 receives the 180-degree phase input signal, and the output of third buffer 40 is connected to the common node. The input of fourth buffer 42 receives the 270-degree phase input signal, and the output of fourth buffer 42 is connected to the common node.
First buffer 36 is driven by a bias current provided by a variable current source 44 and a variable current sink 46 that operate in tandem. That is, the source current (IP0) provided by variable current source 44 is equal to the current (IN0) sunk by variable current sink 46. First buffer 36 outputs a current that represents a proportion of the 0-degree phase input signal determined by this bias current (IP0 and IN0). First buffer 36, variable current source 44 and variable current sink 46 collectively define a first buffer circuit 48.
Likewise, second buffer 38 is driven by a bias current provided by a variable current source 50 and a variable current sink 52 that operate in tandem. That is, the source current (IP90) provided by variable current source 50 is equal to the current (IN90) sunk by variable current sink 52. Second buffer 38 outputs a current that represents a proportion of the 90-degree phase input signal determined by this bias current (IP90 and IN90). Second buffer 38, variable current source 50 and variable current sink 52 collectively define a second buffer circuit 54.
Similarly, third buffer 40 is driven by a bias current provided by a variable current source 56 and a variable current sink 58 that operate in tandem. That is, the source current (IP180) provided by variable current source 56 is equal to the current (IN180) sunk by variable current sink 58. Third buffer 40 outputs a current that represents a proportion of the 180-degree phase input signal determined by this bias current (IP180 and IN180). Third buffer 40, variable current source 56 and variable current sink 58 collectively define a third buffer circuit 60.
In the same manner, fourth buffer 42 is driven by a bias current provided by a variable current source 62 and a variable current sink 64 that operate in tandem. That is, the source current (IP270) provided by variable current source 62 is equal to the current (IN270) sunk by variable current sink 64. Fourth buffer 42 outputs a current that represents a proportion of the 270-degree phase input signal determined by this bias current (IP270 and IN270). Fourth buffer 42, variable current source 62 and variable current sink 64 collectively define a fourth buffer circuit 66.
Fixed-bias phase mixer 16 generates an output phase signal (PH_OUT) in accordance with the following equations:IPA=(1−X)*I_BIAS_FIXED,INA=(1−X)*I_BIAS_FIXED,IPB=X*I_BIAS_FIXED, andINB=X*I_BIAS_FIXED,where IPA and INA represent a first bias current (i.e., a selected one of the following pairs: IP0 and IN0; IP90 and IN90; IP180 and IN180; and IP270 and IN270), where IPB and INB represent a second bias current (i.e., a selected one of the following pairs: IP0 and IN0; IP90 and IN90; IP180 and IN180; and IP270 and IN270), where the selected phase is determined by phase control logic 18 to lie between a phase A and a phase B, where phase A corresponds to the phase input signal that is input to the one of buffers 36-42 driven by IPA and INA (which can be referred to for convenience as "the phase A buffer"), and phase B corresponds to the phase input signal that is input to the one of buffers 36-42 driven by IPB and INB (which can be referred to for convenience as "the phase B buffer"), where X represents the percentage distance between phase A and phase B, and where I_BIAS_FIXED is the sum of the bias current that drives the phase A buffer and the bias current that drives phase B buffer. Note that I_BIAS_FIXED remains fixed, i.e., it does not change in response to any other signal.
In response to the phase selection signal, phase control logic 18 determines phase A and phase B and accordingly determines IPA, INA, IPB and INB. That is, phase control logic 18 sets IPA, INA, IPB and INB by causing the above-described variable current source and sink corresponding to the phase A buffer to be set or adjusted to values of IPA and INA, and causing the above-described variable current sinks corresponding to the phase B buffer to be set or adjusted to values of IPB and INB, respectively. Phase control logic 18 also causes the variable current sources and sinks that do not correspond to the phase A or phase B buffers to be set to a value of zero. With regard to the example described above, in which the phase selection signal indicates a selected phase of 120 degrees and thus in which the selected phase lies between the 90-degree phase input signal (phase A) and the 180-degree phase input signal (phase B), where I_BIAS_FIXED is, for example, 2 mA:IP0=IN0=0,IP90=IN90=(1−0.33)*2=1.33 mA,IP180=IN180=0.33*2=0.67 mA, andIP270=IN270=0.
As illustrated in FIG. 4, each of buffer circuits 48, 54, 60 and 66 includes a number (n) of transistor groups, where a digital control word (C0x . . . Cnx) and its complement (NC0x . . . NCnx) received from phase control logic 18 each have n+1 bits. The "x" in the signal name (e.g., Cn"x") identifies one of the four buffer circuits 48, 54, 60 and 66. The transistors can include P-channel and N-channel metal-oxide semiconductor field-effect transistors, commonly abbreviated as "PFET"s and "NFET"s, respectively. The n+1 transistor groups are identical to each other, and each is controlled by a corresponding bit of the control word. A first exemplary transistor group includes a first PFET 68, a second PFET 70, a first NFET 72, and a second NFET 74; corresponding transistors of a second exemplary transistor group, which is identical to the first exemplary transistor group, are labeled 68′, 70′, 72′ and 74′; corresponding transistors of a third exemplary transistor group, which is identical to the first and second exemplary transistor groups, are labeled 68″, 70″, 72″ and 74″; etc., through the nth transistor group, the corresponding transistors of which are labeled 68′″, 70′″, 72′″ and 74′″. Note that PFETs 68, 68′, 68″, 68′″, etc., collectively define an exemplary one of the variable current sources 44, 50, 56 and 62 described above with regard to FIG. 3. Similarly, note that NFETs 74, 74′, 74″, 74′″, etc., collectively define an exemplary one of the variable current sinks 46, 52, 58 and 64 described above with regard to FIG. 3. By adjusting the control word, phase control logic 18 can adjust the bias with which each of buffers 36-42 is driven to correspond to the control word. When buffers 36-42 are driven with bias currents corresponding to the control word, fixed-bias phase mixer 16 produces a triangle wave-format output phase signal (PH_OUT) having a phase corresponding to the phase selection signal. Logic level converter 20 (FIG. 1) converts the triangle wave-format output phase signal (PH_OUT) into a signal having a squarewave format, such as, for example, CMOS logic voltage levels.

Phase interpolator having adaptively biased phase mixer

Avago Technologies General IP (Singapore) Pte. Ltd.


A pressure contact type connector includes: an upper flat plate portion; a lower flat plate portion which is disposed below the upper flat plate portion; a first spring portion which connects the upper and lower flat plate portions; and a second spring portion which extends upward from the lower flat plate portion and applies a resilient force to the upper flat plate portion, in which the first and second spring portions are wound about the upper flat plate portion when viewed from above in a plan view, and extend so that the spring portions do not interfere with each other when being compressed and extended in the vertical direction, the first spring portion is formed to be bent so that a width dimension is larger than a thickness dimension, and the second spring portion is formed to be bent so that a width dimension is larger than a thickness dimension.

1. Field of the Disclosure
The present disclosure relates to a pressure contact type connector, and particularly, to a pressure contact type connector in which a connection terminal is formed in a spiral shape.
2. Description of the Related Art
In recent years, as means for electrically connecting different substrates housed in an electronic device, use of a structure has increased, in which a pressure contact type connector including a connection terminal having elasticity is provided on one substrate, a contact portion is provided on the other substrate, and the substrates are disposed so that the contact portion and the pressure contact type connector come into pressure-contact with each other. In the pressure contact type connector, the connection terminal is formed in a spiral shape so as to have elasticity. As the pressure contact type connector in which the connection terminal is formed in a spiral shape, a pressure contact type connector disclosed in Japanese Unexamined Patent Application Publication No. 2010-118256 has been known.
Hereinafter, the pressure contact type connector disclosed in Japanese Unexamined Patent Application Publication No. 2010-118256 will be described with reference to FIGS. 13A and 13B. FIGS. 13A and 13B are views showing a structure of a connection terminal 902 of a pressure contact type connector 900, FIG. 13A is a plan view showing an outline of the connection terminal 902, and FIG. 13B is a sectional view showing a section taken along line Z-Z shown in FIG. 13A.
In the pressure contact type connector 900 disclosed in Japanese Unexamined Patent Application Publication No. 2010-118256, the spiral contactor (connector terminal) 902 is spirally formed from the base 902b toward the center of the tip, and includes a tip 902a at the center of the spiral. In addition, the spiral contactor 902 includes a groove 902d formed along a longitudinal direction of the spiral contactor 902 at the center in the width direction of the spiral contactor 902, the center is formed in a planar shape or a convex shape, and the spiral contactor 902 includes a protrusion 902aa on the upper surface of the tip 902a.
In recent years, as a pressure contact type connector, a pressure contact type connector having a mounting area of 2 mm×2 mm or less has been required. However, in the pressure contact type connector 900 disclosed in Japanese Unexamined Patent Application Publication No. 2010-118256, since the spiral contactor 902 is double-spirally formed, it is difficult to decrease a mounting area of the connector. In addition, even when the mounting area decreases by reducing the width of the spiral contactor 902, there is a concern that an elastic force sufficient for obtaining electrically stable connection cannot be obtained.
These and other drawbacks exist.

Pressure contact type connector and manufacturing method of the same


The batter monitoring system is a modified home plate for baseball including a sensor unit to detect whether or not the bat crosses the plate as a hitter swings at a pitched ball and also when a runner crosses the plate. After the pitch, a green light is illuminated to indicate that the batter swung the bat or a red light is illuminated if the batter did not swing the bat. Each player would wear a transmitter which the sensor would detect as it crossed the plate, illuminating the lights and sounding a buzzer to indicate when the device is detected crossing the plate. This allows the umpire to watch the ball coming into the baseman's glove and determine whether the ball arrived before or after he heard the buzzer. The sensor, lights, control unit, and buzzer would be built into the plate, and the plate would be recessed into the ground so that its appearance does not differ from that of a conventional home plate.

1. Field of the Invention
The present invention relates to sports apparatus for use in connection with the game of baseball. The batter monitoring system has particular utility in connection with aiding the umpire in determining if a player has swung his bat over the plate and the precise moment when a runner crosses the plate.
2. Description of the Prior Art
Calls made by umpires in baseball games have been questioned since the game originated. Some of the most questionable calls involve whether or not a batter has rotated past a certain point on a "check swing", which occurs when a batter tries to hold the bat back after he has started to swing. These calls are typically made by the first or third base umpires, depending on whether the batter is right or left handed, and are judgment calls on the part of the umpires. The umpire must determine if the batter will be charged with a strike depending on how far forward the bat was swung before the batter could stop the motion. Heated tempers can result from calls made in these types of situations; therefore, a device that could help the umpire determine if the player's bat has passed forward over the center of the plate would be extremely beneficial to the umpires.
Another type of call which is highly controversial is the umpire's call of a play at home plate. While the calls at all bases are critical, the plays at home plate are crucial because they directly affect the score in the game. Once again, these types of calls are judgment calls by the home plate umpire and are a source of contention with managers and players. Thus, a device which would aid the umpire in determining when a runner crosses the plate would help alleviate the disputes that occur over calls at home plate.
The use of batter monitors for aiding or replacing umpires is known in the prior art. For example, U.S. Pat. No. 5,401,016 to Kenneth W. Heglund, Michael P. O'Dierno, and Travis Scheckel discloses an automatic baseball ball and strike indicator that uses two transducers to detect the presence of an incoming pitch and a series of transducers located on the upper surface of a home plate shaped housing to determine whether the pitched ball is within the strike zone. However, while the size of the strike zone may be changed to accommodate batters of different heights in the Heglund, et al. '016 patent, this would take intervention by an operator of the device and would be time consuming since this procedure would need to occur for nearly every batter. Furthermore, if a ball were to cross through the strike zone and then hit a batter, entitling him to a walk, the Heglund, et al. '016 device would register it as a strike and would need to be cleared and reset so the ball/strike count for the next batter is correct. Finally, the transducers for detecting the incoming pitch and the LEDs for indicating the ball/strike count are located on the front edge of the plate in the Heglund, et al. '016 device where they would be susceptible to being covered with large amounts of loose dirt. Thus, this area of the plate would need to be frequently swept to allow the transducers to work properly and in order for the illumination of the LEDs to be seen.
U.S. Pat. No. 2,121,742 to Thomas F. McLaughlin discloses game apparatus that illuminates the outer edges of a home plate shaped base for improving the visibility of the area. However, the McLaughlin '742 patent does not aid the umpire in making a decision on whether the hitter has swung his bat over the plate. Furthermore, the McLaughlin '742 device does not alert the umpire when a runner has crossed the plate. Lastly, the McLaughlin '742 device utilizes incandescent bulbs for the illumination of the plate. These bulbs would need to be changed frequently, leading to cumbersome and time consuming maintenance since the home plate structure would need to be taken apart to accomplish this task.
Similarly, U.S. Pat. No. Des. 199, 128 to Paul S. Madsen discloses the ornamental design for a baseball home plate. However, the Madsen '128 patent does not provide a mechanism for aiding the umpire in determining if the hitter has swung his bat over the plate. Additionally, the Madsen '128 patent makes no provision for alerting the umpire when a runner crosses the plate.
U.S. Pat. No. 5,676,607 to Ernest A. Stumpf discloses a laser beam strike zone indicator wherein a plurality of adjustable laser beams are directed upwardly from the home plate to define a strike zone for a height of a predetermined batter. However each of the laser beams in the Stumpf '607 patent would need to be adjusted for each new batter, leading to an unacceptable time delay between batters. Moreover, no indication is given in the Stumpf '607 patent as to how the lasers are adjusted. Finally, no information is provided in the Stumpf '607 patent about whether the laser beams can differentiate between a baseball and another object, such as a bat, passing through the strike zone.
Likewise, U.S. Pat. No. 3,341,199 to Paul S. Madsen discloses a baseball and home plate that has stroboscopic properties in conjunction with pitched balls passing thereacross to provide an aid to the umpire in determining whether such pitched balls are balls or strikes. However, utilization of the Madsen '199 device requires the purchase of a large number of baseballs specifically designed for use with the Madsen '199 home plate. This could lead to excessive costs associated with the purchase of these baseballs. Moreover, play in games would need to be halted if a replacement ball was needed and the proper ball could not be located. Finally, the Madsen '199 patent makes no provision for aiding the umpire in determining if the hitter has swung his bat over the plate or for alerting the umpire when a runner crosses the plate.
U.S. Pat. No. 2,440,042 to Ernest Friedman discloses an indicating system for baseball games having bases which are so constructed and arranged as to indicate positively when a player has a foot on the base. However, the Friedman '042 patent requires the use a large number of magnetic devices on the bottoms of the shoes of each player. This could be cost prohibitive if large numbers of teams were to use these bases. Additionally, the Friedman '042 requires players on opposing teams to wear magnetic devices having opposite charges. If any player were accidentally given magnetic devices with the wrong charge, the system would fail to indicate the correct information. Finally, the Friedman '042 device fails to provide a means by which the umpire is aided in determining if a player has swung the bat across the plate in a check swing.
Lastly, U.S. Pat. No. 1,066,773 to Stephen H. Wills discloses a signal base for baseball fields that gives an alarm or signal when a runner reaches and touches a base. This is accomplished with a pair of plates that contact each other when a player steps on the plate, completing a circuit that sounds an alarm or gives some other indication. However, the Wills '773 patent does not take into consideration the fact that the baseman could inadvertently sound the alarm by stepping on the plate while attempting to catch the throw. Moreover, the ball could bounce on the plate and set off the alarm. Lastly, the Wills '773 patent makes no provision for aiding the umpire in calling checked swings by indicating when a hitter has swung his bat over the plate.
While the above-described devices fulfill their respective, particular objectives and requirements, the aforementioned patents do not describe a batter monitoring system that allows the umpire to determine if a player has swung his bat over the plate and the precise moment when a runner crosses the plate. The McLaughlin '742, Madsen '128, Madsen '199, Friedman '042, and Wills '773 patents make no provision for aiding the umpire in determining if the hitter has swung his bat over the plate, such as in a checked swing. Additionally, the McLaughlin '742 and Madsen '128 patent do not provide an indicator when a runner crosses the plate. False indications could be given by the Friedman '042, Wills '773, and the Heglund, et al. '016 devices. If any player wore magnetic devices with the wrong type of charge, the Friedman '042 system would fail to indicate the correct information. The Wills '773 patent fails to consider the fact that a fielder could inadvertently step on the base or that the ball could bounce on the base, both of which would set off the alarm indicating that the runner had touched the base. If a ball were to cross through the strike zone and then hit a batter, entitling him to a walk, the Heglund, et al. '016 device would register it as a strike and would need to be cleared and reset so the ball/strike count for the next batter was correct. Furthermore, no information is provided in the Stumpf '607 patent about whether the laser beams can differentiate between a baseball and another object, such as a bat, passing through the strike zone. Use of the Madsen '199 and Friedman '042 devices requires the purchase of large numbers of specialty items, such as striped baseballs for use with the Madsen '199 device and magnetic devices for use with the Friedman '042 device. Moreover, play in games using the Madsen '199 device would need to be halted if a replacement ball was needed and the proper ball could not be located. The McLaughlin '742 patent utilizes incandescent bulbs for the illumination of the plate. These bulbs would need to be changed frequently, leading to cumbersome and time consuming maintenance since the home plate structure would need to be taken apart to accomplish this task. Additionally, the transducers for detecting the incoming pitch and the LEDs for indicating the ball/strike count are located on the front edge of the plate in the Heglund, et al. '016 device where they would be susceptible to being covered with large amounts of loose dirt. Thus, this area of the plate would need to be frequently swept to allow the transducers to work properly and in order for the illumination of the LEDs to be seen. Furthermore, while the size of the strike zone may be changed to accommodate batters of different heights in the Heglund, et al. '016 and Stumpf '607 patents, this would take intervention by an operator of the device and would be time consuming since this procedure would need to occur for nearly every batter. Finally, no indication is given in the Stumpf '607 patent as to how the lasers are adjusted.
Therefore, a need exists for a new and improved batter monitoring system that can be used for aiding the home plate umpire in making calls. In this regard, the present invention substantially fulfills this need. In this respect, the batter monitoring system according to the present invention substantially departs from the conventional concepts and designs of the prior art, and in doing so provides an apparatus primarily developed for the purpose of aiding the umpire in determining if a player has swung his bat over the plate and the precise moment when a runner crosses the plate.


A non-contact, extractive sampling system and method is provided for measuring the exhaust gas composition and fine particle composition of exhaust emissions of various types of vehicles under actual operating conditions. A portion (or sample) of an exhaust plume of a vehicle is pulled or extracted through an extraction sampling tube, via a vacuum pump, to a remote trace gas detection system where the concentration of one or more constituents present in the sample of exhaust plume may be measured. In this regard, the invention enables vehicle emissions measurements to be made at a location remote from roadway, rather than using known, “cross-path” remote emissions sensing systems.

Systems and methods for monitoring the exhaust gas composition and fine particle composition of exhaust emissions of various types of vehicles are known. For example, with regard to automobiles, it is common for emissions inspection stations (or automotive repair facilities) to utilize dynamometers for controlled engine loading tests for the purposes of exhaust emission measurement. One drawback associated with dynamometer testing, however, is that the measurements acquired often do not represent emissions under actual operating conditions when automobiles are in motion on a roadway or other driving surface.
To remedy these and other drawbacks associated with dynamometer testing, remote emissions sensing systems have been developed to remotely monitor the exhaust gas composition of automobiles traveling past "test sites" located along streets or highways. Examples of remote emissions sensing (or "cross-road") systems are described in, for example, U.S. Pat. Nos. 5,210,702, 5,319,199, 5,401,967, 5,591,975, 5,726,450, 5,797,682, 5,831,267, and 5,877,862, each of which is hereby incorporated herein by reference in its entirety.
Despite steady advances in the sophistication and robustness of remote emissions sensing systems, the implementation of some such systems may be somewhat time and/or labor intensive. For example, the equipment comprising a remote emissions sensing system is often transported to a test site in a vehicle (e.g., a van), assembled for a testing session, calibrated, disassembled after the testing session, and either transported to a new test site or returned to a central facility where acquired emissions (and other) data may be processed.
Moreover, some remote emissions sensing systems remain susceptible to erroneous readings or inconsistent results. Unfortunately, such drawbacks can sometimes lead to relatively high incidences of discarded data or relatively high incidences of "flagged" test results, which indicate suspect results.
In addition, existing remote emissions sensing systems often utilize external mirrors to direct light beams through vehicle plumes. These exposed mirrors require careful alignment and are subject to alignment drift, degradation from the elements, and/or vandalism. This may present difficulties when deploying such systems without an operator, or when deploying them under adverse weather conditions.
Additionally, existing remote sensing systems can be limited in the number of molecular species that they can monitor with sufficient sensitivity, and in the type of detailed particulate information that they can provide. Current commercial instruments monitor only a few molecular species which typically do not include "air toxics" like formaldehyde, acrolein and 1,3-butadiene. Also, some of these monitors provide only an opacity measurement for particles. An opacity measurement provides little or no information regarding the size distributions or chemical compositions of particulate matter.
These and other problems can reduce the benefits of remote emissions sensing systems.

Extractive sampling system and method for measuring one or more molecular species