WO2015173035A1 - Composés herbicides - Google Patents

Composés herbicides Download PDF

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Publication number
WO2015173035A1
WO2015173035A1 PCT/EP2015/059615 EP2015059615W WO2015173035A1 WO 2015173035 A1 WO2015173035 A1 WO 2015173035A1 EP 2015059615 W EP2015059615 W EP 2015059615W WO 2015173035 A1 WO2015173035 A1 WO 2015173035A1
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formula
alkyl
substituted
crc
compound
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PCT/EP2015/059615
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English (en)
Inventor
Stephen Edward Shanahan
Alan Joseph Hennessy
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Syngenta Participations Ag
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Priority claimed from GBGB1408571.6A external-priority patent/GB201408571D0/en
Priority claimed from GB201417980A external-priority patent/GB201417980D0/en
Application filed by Syngenta Participations Ag filed Critical Syngenta Participations Ag
Publication of WO2015173035A1 publication Critical patent/WO2015173035A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system

Definitions

  • the present invention relates to 8H-thiopyrano[3,4-b]pyridine 7,7-dioxide derivatives, to processes and intermediates for making these compounds, to herbicidal compositions comprising these compounds and to methods of using these compounds to control plant growth.
  • WO2009/063180 describes 1 H-2-thia-1 ,5,8-triazanaphtalene-2,2-dioxides with herbicidal and plant growth inhibiting properties.
  • WO2010/130970 describes 6,6-dioxo-6-thia-1 ,4-diaza-naphthalene derivatives with herbicidal properties, whilst WO2012/062531 describes the potential use of certain 5H- quinoxaline derivatives as herbicidal agents/plant growth inhibitors.
  • the present invention is based on the finding that 8H-thiopyrano[3,4-b]pyridine 7,7- dioxide derivatives have surprisingly good herbicidal properties.
  • the invention therefore provides a compound of formula (I)
  • R 1 , R 2 and R 12 are independently hydrogen, halogen, cyano, CrC 8 alkyl, CrC 8 haloalkyl, hydroxy, CrC 8 alkoxy-, thiol or CrC 8 alkylthio-;
  • R 3a and R 3b are independently hydrogen, halogen, cyano, Ci-C 8 alkyl, Ci-C 8 alkoxy-CrC 4 alkyl-, Ci-C 8 haloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 haloalkenyl, C 2 -C 8 alkynyl, C 2 -C 8 haloalkynyl, C 3 -Ci 0 cycloalkyl, C 3 -Ci 0 cycloalkyl-Ci-C 4 alkyl-, heterocyclyl, heterocyclyl-Ci-C 4 alkyl-, or Ci-C 8 alkoxycarbonyl-; or R 3a and R 3b
  • each R 6 is independently halogen, cyano, nitro, Ci-C 8 alkyl, Ci-C 8 alkoxy-CrC 4 alkyl-, Ci-C 8 haloalkyl, Ci-C 8 haloalkoxy-Ci-C 4 alkyl-, hydroxy, Ci-C 8 alkoxy-, Ci-C 8 haloalkoxy-, thiol, d- C 8 alkylthio-, Ci-C 8 haloalkylthio-, Ci-C 8 alkylsulfinyl-, Ci-C 8 haloalkylsulfinyl-, Ci-C 8 alkylsulfo-nyl-, CrC 8 haloalkylsulfonyl-, amino, /V-Ci-C 8 alkylcarbonylamino-, /V-Ci-C 8 alkyl- /V-Ci-C 8 alkylcarbonylamino-, /V-Ci
  • R 1 , R 2 and R 12 are independently hydrogen, halogen, cyano, Ci-C 8 alkyl, Ci-C 8 haloalkyi, hydroxy, Ci- Cs alkoxy-, thiol or Ci-C 8 alkylthio-;
  • R 4 is aryl or aryl substituted by one to five R 6 , or heteroaryl or heteroaryl substituted by one to five R 6 ;
  • each R 6 is independently halogen, cyano, nitro, Ci-C 8 alkyl, Ci-C 8 alkoxy-CrC 4 alkyl-, Ci-C 8 haloalkyi, Ci-C 8 haloalkoxy-Ci-C 4 alkyl-, hydroxy, Ci-C 8 alkoxy-, Ci-C 8 haloalkoxy-, thiol, Ci-C 8 alkylthio-, Ci-C 8 haloalkylthio-, Ci-C 8 alkylsul
  • R 1 , R 2 and R 12 are independently hydrogen, halogen, cyano, CrC 8 alkyl, CrC 8 haloalkyi, hydroxy, CrC 8 alkoxy-, thiol or CrC 8 alkylthio-;
  • R 3a and R 3b are independently hydrogen, halogen, cyano, Ci-C 8 alkyl, Ci-C 8 alkoxy-CrC 4 alkyl-, Ci-C 8 haloalkyi, C 2 -C 8 alkenyl, C 2 -C 8 halo alkenyl, C 2 -C 8 alkynyl, C 2 -C 8 haloalkynyl, C 3 -Ci 0 cycloalkyl, C 3 -Ci 0 cycloalkyl-Ci-C 4 alkyl-, heterocyclyl, heterocyclyl-Ci-C 4 alkyl-,
  • R 1 , R 2 and R 12 are independently hydrogen, halogen, cyano, Ci-C 8 alkyl, Ci-C 8 haloalkyi, hydroxy, CrC 8 alkoxy-, thiol or CrC 8 alkylthio-;
  • R 4 is aryl or aryl substituted by one to five R 6 , or heteroaryl or heteroaryl substituted by one to five R 6 ;
  • each R 6 is independently halogen, cyano, nitro, Ci-C 8 alkyl, CrC 8 alkoxy-CrC 4 alkyl-, CrC 8 haloalkyl, CrC 8 haloalkoxy-Ci-C 4 alkyl-, hydroxy, Ci-C 8 alkoxy-, Ci-C 8 haloalkoxy-, thiol, Ci-C 8 alkylthio-, d- C 8 haloalkylthio-, Ci-C 8 alkylsul
  • the compounds of formula (I) and (10) may exist in different geometric or optical isomers or tautomeric forms.
  • This invention covers all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.
  • atropisomers are obtained in those cases where the rotation of the R 4 group is restricted, for example in those cases where the R 4 group has at least one o f/?o-substituent.
  • a compound of formula (la) i.e. a compound of formula (I) where R 5 is hydroxy
  • a compound of formula (la) where R 5 is hydroxy can be drawn in two tautomeric forms.
  • the compounds of the invention may contain one or more asymmetric carbon atoms, for example, at the -CR 3a R 3b - group, and may exist as enantiomers (or as pairs of diastereoisomers) or as mixtures of such.
  • Alkyl groups can be in the form of a straight or branched chain and are, for example, methyl, ethyl, propyl, prop-2-yl, butyl, but-2-yl, 2-methyl-prop-1 -yl or 2-methyl- prop-2-yl.
  • the alkyl groups are preferably CrC 6 , more preferably CrC 4 , most preferably C1-C3 alkyl groups.
  • Alkenyl groups can be in the form of straight or branched chains, and can be, where appropriate, of either the (E)- or (Z)-configuration. Examples are vinyl and allyl.
  • the alkenyl groups are preferably C 2 -C 6 , more preferably C 2 -C 4 , most preferably C 2 -C 3 alkenyl groups.
  • Alkynyl groups can be in the form of straight or branched chains. Examples are ethynyl and propargyl.
  • the alkynyl groups are preferably C 2 -C 6 , more preferably C 2 -C 4 , most preferably C 2 -C 3 alkynyl groups.
  • Halogen is fluorine, chlorine, bromine or iodine.
  • Haloalkyl groups are alkyl groups which are substituted by one or more of the same or different halogen atoms and are, for example, difluoromethyl, trifluoromethyl, chlorodifluoromethyl or 2,2,2-trifluoro-ethyl.
  • Haloalkenyl groups are alkenyl groups which are substituted by one or more of the same or different halogen atoms and are, for example, 2,2-difluoro-vinyl or 1 ,2-dichloro-2- fluoro-vinyl.
  • Haloalkynyl groups are alkynyl groups which are substituted by one or more of the same or different halogen atoms and are, for example, 1 -chloro-prop-2-ynyl.
  • Cycloalkyi groups and carbocyclic rings can be in mono- or bi-cyclic form and are, for example, cyclopropyl, cyclobutyl, cyclohexyl and bicyclo[2.2.1 ]hept-2-yl.
  • the cycloalkyi groups are preferably C 3 -C 8 , more preferably C 3 -C 6 cycloalkyi groups.
  • Heterocyclyl groups and heterocyclic rings are ring systems containing at least one heteroatom and can be in mono- or bi-cyclic form.
  • heterocyclyl groups will contain up to two heteroatoms which will preferably be chosen from nitrogen, oxygen and sulfur.
  • heterocyclic groups include oxetanyl, thietanyl, azetidinyl and 7-oxa-bicyclo[2.2.1]hept-2- yl.
  • Heterocyclyl groups containing a single oxygen atom as heteroatom are most preferred.
  • the heterocyclyl groups are preferably 3- to 8-membered, more preferably 3- to 6- membered rings.
  • Aryl groups are aromatic ring systems which can be in mono-, bi- or tricyclic form. Examples of such rings include phenyl, naphthyl, anthracenyl, indenyl or phenanthrenyl. Preferred aryl groups are phenyl and naphthyl, phenyl being most preferred. Where an aryl moiety is substituted, the aryl moiety is preferably substituted by one to four substituents, most preferably by one to three substituents.
  • Heteroaryl groups are aromatic ring systems containing at least one heteroatom and consisting either of a single ring or of two or more fused rings.
  • single rings will contain up to three heteroatoms which will preferably be chosen from nitrogen, oxygen and sulfur.
  • monocyclic groups include pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, furanyl, thiophenyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl and thiadiazolyl.
  • bicyclic systems will contain up to four heteroatoms which will preferably be chosen from nitrogen, oxygen and sulfur.
  • bicyclic groups include quinolinyl, cinnolinyl, quinoxalinyl, indolyl, indazolyl, benzimidazolyl, benzothiophenyl and benzothiadiazolyl.
  • Monocyclic heteroaryl groups are preferred, pyridyl being most preferred.
  • the heteroaryl moiety is preferably substituted by one to four substituents, most preferably by one to three substituents.
  • Metabolism means the conversion or breakdown of a substance from one form to another by a living organism, in particular in a plant (in planta).
  • Salts comprise a charged version of a compound of formula (I) and a counter ion of the opposite charge.
  • the compounds of formula (I) can have a negative charge, for example, on an oxygen atom of a hydroxy group, if the hydroxy group is deprotonated with a base.
  • Suitable bases include ammonia.
  • Suitable cationic counter ions include, for example, alkali metals such as sodium or potassium, or alkaline earth metals such as magnesium and calcium, or quaternary ammonium bases such as ammonium and tetramethylammonium.
  • the compounds of formula (I) can have a positive charge, for example, on the nitrogen atom in a nitrogen-containing heteroaryl group, if the nitrogen atom is quarternised by protonation with an organic or inorganic acid, or if the nitrogen atom is quarternised by alkylation for example with a methyl group, or if the nitrogen atom is quarternised by amination.
  • Suitable anionic counter ions include, for example, the dissociated acid anion or a simple anion such as hydroxide, chloride or bromide.
  • the compounds of formula (I) according to the invention also include hydrates which may be formed, for example, during salt formation.
  • /V-oxides are compounds of formula (I) where a nitrogen atom has been oxidised.
  • /V-oxides are compounds of formula (I) where the nitrogen atom in a nitrogen- containing heteroaryl group has been oxidised.
  • R 1 , R 2 , R 3a , R 3b , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 are, in any combination, as set out below and a compound of formula (I), (6), (9) or (10) according to the invention may comprise any combination of said values.
  • a compound of formula (I), (6), (9) or (10) according to the invention may comprise any combination of said values.
  • values for any specified set of embodiments may combined with values for any other set of embodiments where such combinations are not mutually exclusive.
  • R 1 is hydrogen, halogen, d-C 3 alkyl, CrC 3 alkoxy, more preferably hydrogen, chloro, methyl, or methoxy, most preferably hydrogen.
  • R 2 is hydrogen, halogen, CrC 3 alkyl, or CrC 3 alkoxy, more preferably hydrogen, chloro, methyl, or methoxy, most preferably hydrogen.
  • R 12 is hydrogen, halogen, Ci-C 3 alkyl, or Ci-C 3 alkoxy, more preferably hydrogen, chloro, methyl, or methoxy, most preferably hydrogen or methoxy.
  • R 3a is hydrogen, halogen, CrC 8 alkyl, CrC 8 haloalkyl or C 2 -C 8 alkynyl, more preferably hydrogen.
  • R 3a groups include hydrogen, fluoro, methyl, ethyl, 2,2-difluoro-ethyl and propargyl.
  • R 3b is hydrogen, halogen, CrC 8 alkyl, Ci-C 8 haloalkyl or C 2 -C 8 alkynyl, more preferably hydrogen.
  • R 3b groups include hydrogen, fluoro, methyl, ethyl, 2,2-difluoro-ethyl and propargyl.
  • one of R 3a or R 3b is hydrogen.
  • both R 3a and R 3b are hydrogen.
  • both R 3a and R 3b are fluoro.
  • both R 3a is fluoro and R 3b is hydrogen.
  • R 3a is methyl and R 3b is hydrogen.
  • both R 3a and R 3b are methyl.
  • R 3a is 2,2-difluoro-ethyl and R 3b is hydrogen.
  • R 3a is 2,2-difluoro-ethyl and R 3b is methyl.
  • R 3a and R 3b together with the carbon atom they are attached to join to form cyclopropyl.
  • R 4 is phenyl or phenyl substituted by one to five (preferably two to five, more preferably two to three) R 6 , or heteroaryl or heteroaryl substituted by one to five(preferably two to five, more preferably two to three) R 6 (where heteroaryl is pyridyl, pyrimidinyl, pyrazolyl, triazolyl, thiophenyl, isoxazolyl, oxadiazolyl or thiazolyl); more preferably phenyl or phenyl substituted by two to five R 6 , or pyridyl or pyridyl substituted by two to three R 6 ; most preferably phenyl or phenyl substituted by two to three R 6 .
  • R 4 is phenyl substituted by at least two R 6 (more preferably two or three R 6 ), it is preferred that for at least two of said substitutents R 6 , each is located ortho with respect to the point of attachment to the thiopyranopyridine moiety. This is particularly the case when both R 3a and R 3b are hydrogen.
  • each R 6 is independently halogen, cyano, nitro, CrC 8 alkyl, Ci-C 8 haloalkyl, CrC 8 alkoxy-, benzyloxy or benzyloxy substituted by 1 to 5 (more preferably 1 to 3, and most prefereably 1 -2) R 7 , CrC 8 haloalkoxy-, Ci-C 8 alkylthio-, or Ci-C 8 haloalkylthio-, more preferably halogen, Ci-C 8 alkyl, Ci-C 8 haloalkyl, Ci-C 8 alkoxy- or Ci-C 8 haloalkoxy-.
  • R 6 groups include bromo, chloro, fluoro, methyl, ethyl, trifluoromethyl, methoxy, trifluoromethoxy, benzyloxy or benzyloxy substituted by 1 to 5 (more preferably 1 to 3, and most prefereably 1 -2) R 7 .
  • R 7 groups examples include bromo, chloro, fluoro, methyl, ethyl, trifluoromethyl, methoxy and trifluoromethoxy.
  • R 4 is 2,5-bis-(trifluoromethyl)-phenyk
  • R 4 is 3-bromo-2-chloro-6-fluoro-phenyk
  • R 4 is 2-bromo-5-chloro-phenyk
  • R 4 is 2-bromo-phenyk
  • R 4 is 4-bromo-2-trifluoromethyl-phenyk
  • R 4 is 2-chloro-3,6-difluoro-phenyk
  • R 4 is 2-chloro-6-fluoro-3-trifluoromethyl-phenyl
  • R 4 is 4-chloro-2-methylsulfonyl-phenyk
  • R 4 is 2-chloro-5-trifluoromethyl-phenyk
  • R 4 is 2-chloro-6-trifluoromethyl-phenyk
  • R 4 is 4-chloro-2-trifluoromethyl-phenyk
  • R 4 is 5-chloro-2-trifluoromethyl-phenyk
  • R 4 is 2,3-dichloro-6-fluoro-phenyk
  • R 4 is 2,6-dichloro-phenyk
  • R 4 is 2,6-dichloro-3-trifluoromethyl-phenyk
  • R 4 is 3,5-difluoro-2-trifluoromethyl-phenyl-.
  • R 4 is 2-ethyl-4-(4'-chloro-phenyl)-phenyl-.
  • R 4 is 2,3,6-trichloro-phenyl-.
  • R 4 is 2-trifluoromethyl-phenyk
  • R 4 is 2,4,6-trimethyl-phenyl-.
  • R 4 is 2-benzyloxy-3,6-dichloro-phenyl. In one embodiment R 4 is 3,6-dichloro-2-[3,4-dichlorophenyl)methoxy]phenyl.
  • R 4 is 3,6-dichloro-2-[4-methoxyphenyl)methoxy]phenyl.
  • R 4 is 3,6-dichloro-2-[4-methylphenyl)methoxy]phenyl.
  • R 4 is 3,6-dichloro-2-[4-trifluoromethylphenyl)methoxy]phenyl.
  • R 4 is 3,6-dichloro-2-[4-chlorophenyl)methoxy]phenyl.
  • R 4 is 2-benzyloxy-3-chloro-6-fluoro-phenyl.
  • R 4 is 3-chloro-6-fluoro-2-[3,4-dichlorophenyl)methoxy]phenyl
  • R 4 is 3-chloro-6-fluoro-2-[4-methoxyphenyl)methoxy]phenyl.
  • R 4 is 3-chloro-6-fluoro-2-[4-methylphenyl)methoxy]phenyl.
  • R 4 is 3-chloro-6-fluoro-2-[4-trifluoromethylphenyl)methoxy.]
  • R 4 is 3-chloro-6-fluoro-2-[4-chlorophenyl)methoxy.]
  • R 4 is 2-benzyloxy-6-chloro-phenyl.
  • R 4 is 2-benzyloxy-6-fluoro-phenyl.
  • R 4 is 2-benzyloxy-3,6-difluoro-phenyl.
  • R 4 is 3-chloro-6-trifluoromethyl-phenyl
  • R 4 is 3-fluoro-6-trifluoromethyl-phenyl.
  • R 4 is phenyl substituted by two or three R 6 , wherein 2 of said R 6 substitutents are situated ortho with respect to the point of attachment to the thiopyranopyridine moiety, and one of said ortho R 6 substituents is benzyloxy, or benzyloxy substituted by 1-5 (more preferably 1 to 3, and most preferably 1- 2) R 7 .
  • R 5 may be hydroxyl or any group capable of being metabolised to a hydroxyl group.
  • the skilled man will be familiar with the types of groups which are metabolisable, and a comprehensive description of such groups is given for example in WO2008/071918 (from line 26 on page 6 to line 23 on page 7).
  • R 5 is hydroxyl, -OR 8 , or -OC(0)R 8 , wherein R 8 is selected from the group consisting of CrC 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C C 6 alkyl-S-, C C 6 alkoxy, -NR 9 R 10 and phenyl optionally substituted by one or more R 13 .
  • R 5 is hydroxyl, CrC 6 alkoxy-, C 2 -C 6 alkenoxy-, C 2 -C 6 alkynoxy-, CrC 6 alkysulfonyloxy-, benzyloxy-, -OC(0)-R 8 .
  • R 9 and R 10 are independently selected from the group consisting of Ci-C 6 alkyl, CrC 6 alkoxy-; or they can together form a morpholinyl ring.
  • R 9 and R 10 are independently selected from the group consisting of C1-C4 alkyl, d-C 4 alkoxy-; or they can together form a morpholinyl ring. More preferably R 9 and R 10 are each independently selected from the group consisting of methyl, ethyl, propyl, methoxy, ethoxy and propoxy.
  • each R 13 is independently selected from the group consisting of halogen, cyano, nitro, CrC 3 alkyl, d-C 3 haloalkyl, CrC 3 alkoxy and CrC 3 haloalkoxy.
  • R 8 is C C 4 alkyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl,-Ci-C 3 alkoxy, or -NR 9 R 10 wherein R 9 and R 10 together form a morpholinyl ring.
  • R 5 is hydroxyl or -OC(0)-R 8 ' wherein R 8 is C C 4 alkyl
  • R 5 is hydroxyl or -OC(0)-R 8 ' wherein R 8 is isopropyl, t-butyl, methyl, ethyl, propargyl or methoxy. However, it is particularly preferred that R 5 is hydroxyl.
  • R 1 and R 2 are hydrogen
  • R 12 is hydrogen or methoxy
  • R and R are both methyl or R and R together with the carbon atom to which they are attached form a cyclopropyl ring
  • R 5 is hydroxyl
  • R 4 is phenyl substituted by 2 or 3 R 6 independently selected from halogen, Ci-C 3 haloalkyl, benzyloxy, or benzyloxy substituted by 1 -2 R 7 .
  • R 12 is hydrogen and each R 6 is independently chloro, fluoro, bromo, methyl, trifluoromethyl or benzyloxy, and two of said R 6 are each situatedortho with respect to the point of attachment to the thiopyranopyridine moiety.
  • R 1 , R 2 , R 4 and R 12 are the same as defined above in respect of a compound of formula (I), and in the case of a compound of formula (6) and a compound of formula (9), it is preferred that R 11 is Ci-C 4 alkyl, in particular methyl or ethyl.
  • R 3(a) and R 3(b) are both hydrogen; such compounds may be depicted as compounds of formula (9a)
  • R 1 , R 2 , R 12 , R 4 and R 11 are as defined supra.
  • R 4 is phenyl substituted by at least two R 6 , it is preferred that for at least two of said substituents R 6 , each is located ortho with respect to its point of attachment.
  • Table 1 provides 29 compounds of formula (lb), where R 4 has the values listed in Table 1 .
  • Compounds of formula (lb) are compounds of formula (I) where R 1 , R 2 , R 3a and R 3b are each hydrogen and R 5 is hydroxy.
  • Table 2 provides 29 compounds of formula (Ic), where R 4 has the values listed in Table 2.
  • Compounds of formula (Ic) are compounds of formula (I) where R 1 , R 2 and R 3a are each hydrogen; R 3b is methyl; and R 5 is hydroxy.
  • Table 3 provides 29 compounds of formula (Id), where R has the values listed in Table 3.
  • Compounds of formula (Id) are compounds of formula (I) where R 1 and R 2 are each hydrogen; R 3a and R 3b are each methyl; and R 5 is hydroxy.
  • Compounds of formula (le) are compounds of formula (I) where R 1 , R 2 and R 3a are each hydrogen; R 3b is ethyl; and R 5 is hydroxy.
  • Table 5 provides 29 compounds of formula (If), where R 4 has the values listed in Table 5.
  • Compounds of formula (If) are compounds of formula (I) where R 1 and R 2 are each hydrogen; R 3a is methyl; R 3b is propargyl; and R 5 is hydroxy.
  • Table 6 provides 29 compounds of formula (Ig), where R 4 has the values listed in Table 6.
  • Compounds of formula (Ig) are compounds of formula (I) where R 1 , R 2 and R 3a are each hydrogen; R 3b is propargyl; and R 5 is hydroxy.
  • Table 7 provides 29 compounds of formula (Ih), where R 4 has the values listed in Table 7.
  • Compounds of formula (Ih) are compounds of formula (I) where R 1 , R 2 and R 3a are each hydrogen; R 3b is F 2 HC-H 2 C-; and R 5 is hydroxy.
  • Table 8 provides 29 compounds of formula (li), where R 4 has the values listed in Table 8.
  • Compounds of formula (li) are compounds of formula (I) where R 1 and R 2 are each hydrogen; R 3a and R 3b and the carbon atom to which they are both joined form cyclopropyl; and R 5 is hydroxy.
  • a carboxylic ester of formula (3) where R 1 and R 2 are as defined for a compound of formula (I) and R 11 is CrC 8 alkyl can be made by reacting an acid derivative of formula (2), where R 1 and R 2 are as defined for a compound of formula (I) and Y is a halogen atom or a hydroxy group, with an alcohol R 11 OH where R 11 is CrC 8 alkyl, as shown in Scheme 1.
  • Y is a halogen atom, such as a chloro atom
  • the reaction can conveniently be carried out in the presence of a base, such as triethylamine or pyridine, in a solvent, such as acetonitrile or dichloromethane, optionally using microwave heating.
  • a carboxylic ester of formula (4) where R 1 and R 2 are as defined for a compound of formula (I) and R 11 is as defined in 1 ) can be made by reacting a carboxylic ester of formula (3) as defined in 1 ) with a halogenating agent, such as chlorine, bromine, N- chlorosuccinimide, /V-bromosuccinimide, or trichloroisocyanuric acid, optionally in the presence of light, or a radical initiator, or both.
  • radical initiators are 2,2'- azobis(2-methylpropionitrile) ("AIBN”) or benzoyl peroxide.
  • An example of a suitable light source is a 500 watt tungsten halogen lamp.
  • the preparation is carried out in a solvent, such as carbon tetrachloride or dichloromethane, at a temperature between 0 °C and the reflux temperature of the solvent.
  • a thiouronium salt of formula (5) where R 1 and R 2 are as defined for a compound of formula (I) and R 11 is as defined in 1 ) can be made by reacting a carboxylic ester of formula (4) as defined in 2) with thiourea in a solvent, such as tetrahydrofuran, 2-butanone or dichloromethane, optionally using microwave heating, as shown in Scheme 2.
  • a solvent such as tetrahydrofuran, 2-butanone or dichloromethane
  • a thioether of formula (6) where R 1 , R 2 and R 4 are as defined for a compound of formula (I) and R 11 is as defined in 1 ) can be made by reacting a thiouronium salt of formula (5) as defined in 3) with a benzylic compound of formula (7) where R 4 is as defined for a compound of formula (I) and LG is a leaving group, for example a halide [such as chloride, bromide or iodide], tosylate, mesylate or triflate, in the presence of a base [such as potassium carbonate] in a solvent [such as acetonitrile or /V,/V-dimethylformamide] and optionally using microwave heating.
  • a base such as potassium carbonate
  • solvent such as acetonitrile or /V,/V-dimethylformamide
  • a thioether of formula (6) as defined in 4) can be made by reacting a carboxylic ester of formula (4) as defined in 2) with a thiouronium salt of formula (8) where R 4 is as defined for a compound of formula (I), in the presence of a base, such as potassium carbonate, in a solvent, such as acetonitrile or /V,/V-dimethylformamide, optionally using microwave heating.
  • Thiouronium salts of formula (8) can be made by reacting a benzylic compound of formula (7) as defined in 4) with thiourea in a solvent, such as ethanol, tetrahydrofuran, 2-butanone or dichloromethane, optionally using microwave heating.
  • benzylic compounds of formula (7) are commercially available or can be made by methods known to a person skilled in the art.
  • Certain arylmethoxy- substituted compounds (7), namely subset (7a) can be prepared according to Scheme 7.
  • a sulfone of formula (9) where R 1 , R 2 and R 4 are as defined for a compound of formula (I) and R 11 is as defined in 1 ) can be made by reacting a thioether of formula (6) as defined in 4) with an oxidising agent, in a compatible solvent, preferably at ambient temperature, as shown in Scheme 3.
  • oxidising agent/solvent combinations are 3-chloroperoxybenzoic acid ("mCPBA") in dichloromethane, or aqueous hydrogen peroxide in acetic acid.
  • a hydroxy-bicycle of formula (10) where R 1 , R 2 and R 4 are as defined for a compound of formula (I) can be made by reacting a compound of formula (9) as defined in 6) with a base, such as potassium carbonate or 1 ,8-Diazabicyclo[5.4.0]undec-7-ene (“DBU”), in a solvent, such as acetonitrile or /V,/V-dimethylformamide, optionally using microwave heating.
  • a base such as potassium carbonate or 1 ,8-Diazabicyclo[5.4.0]undec-7-ene (“DBU”)
  • a bicycle of formula (1 1 ) where R 1 , R 2 and R 4 are as defined for a compound of formula (I), X is defined as CrC 6 alkylsulfonyl, -R 8 or -C(0)R 8 and R 8 is as defined for a compound of formula (I), can be made by reacting a hydroxy-bicycle of formula (10) as defined in 7) with a compound of formula X-LG wherein X is as defined above and LG is as defined in 4) in the presence of a base, such as triethylamine, pyridine or potassium ie f-butoxide, in a solvent, such as dichloromethane, tetrahydrofuran or toluene, optionally using microwave heating, as shown in Scheme 4.
  • a base such as triethylamine, pyridine or potassium ie f-butoxide
  • a nucleophilic catalyst such as 4-(dimethylamino)pyridine (DMAP) can be employed in sub-stoichiometric amounts.
  • X is methyl
  • methyl iodide can conveniently be used as reagent.
  • the corresponding bromide such as benzyl bromide
  • X is -C(0)R 8 and R 8 is isopropyl, ie f-butyl, ethoxy, or -S-ethyl
  • the corresponding chloride such as pivaloyl chloride
  • X is CrC 6 alkylsulfonyl
  • alkylsulfonyl chlorides such as mesyl chloride, can conveniently be used as reagent.
  • a substituted bicycle of formula (12) where R 1 , R 2 , R 3a and R 4 are as defined for a compound of formula (I) and X is as defined in 8) can be made by reacting a methylene compound of formula (1 1 ) as defined in 8) with a base [such as lithium diisopropylamide, 1 ,8-diazabicyclo[5.4.0]undec-7-ene, potassium ie f-butoxide, potassium carbonate or cesium carbonate] and an electrophile [such as an alkylating agent, a halogenating agent or a cyanating agent], in a solvent [such as tetrahydrofuran, dimethylsulfoxide or N,N- dimethylformamide], optionally using microwave heating.
  • a base such as lithium diisopropylamide, 1 ,8-diazabicyclo[5.4.0]undec-7-ene, potassium ie f-butoxide, potassium carbonate or cesium carbonate
  • Suitable alkylating agents are, for example, alkyl halides, such as methyl iodide, for making a compound where R 3a is C C 8 alkyl, in particular methyl.
  • Suitable halogenating agents are, for example, 4-iodotoluene difluoride (CAS RN 371 -1 1 -9) or /V-fluorobenzenesulfonimide ("NFSI”), /V-chlorosuccinimide (“NCS”), /V-bromosuccinimide (“NBS”), and /V-iodosuccinimide (“NIS”), for making a compound where R 3a is F, CI, Br, or I, respectively.
  • Suitable cyanating agents are, for example, cyanogen bromide, 1 -cyanobenzotriazole, phenyl cyanate ("PhOCN”) or tosyl cyanide for making a compound where R 3a is cyano.
  • a gem-disubstituted bicycle of formula (13) where R 1 , R 2 , R 3a , R 3b and R 4 are as defined for a compound of formula (I) and X is as defined in 8) can be made by reacting a compound of formula (1 1 ) as defined in 8) typically with two equivalents of base and two equivalents of electrophile as defined under 9) applied simultaneously or successively.
  • R 3a and R 3b are the same it is preferred to carry out the reactions simultaneously, without isolation of the intermediate.
  • R 3a and R 3b are different it is preferred to carry out the reactions successively, optionally isolating the intermediate.
  • a hydroxy-bicycle of formula (14) where R 1 , R 2 , R 3a , R 3b and R 4 are as defined for a compound of formula (I) or a hydroxy-bicycle of formula (15) where R 1 , R 2 , R 3a and R 4 are as defined for a compound of formula (I) can be made by reacting a gem-disubstituted bicycle of formula (13) as defined in 10) or a mono-substituted bicycle of formula (12) as defined in 9), with base, such as lithium hydroxide or potassium carbonate, in a solvent, such as tetrahydrofuran or dimethylsulfoxide, with or without the presence of water, optionally using microwave heating.
  • base such as lithium hydroxide or potassium carbonate
  • (14) or (15) may be prepared by treating (13) or (12) as appropriate with an acid, such as concentrated sulfuric acid, with or without a solvent, optionally using microwave heating. Since all the subsequent transformations of (1 1 ) in Scheme 4 may on occasions be facilitated by the same pairings of base and solvent, direct preparation of (14) or (15) is sometimes observed in the attempted preparation of (13) or (12).
  • a sulfone of formula (16) where R 1 , R 2 , R 3a and R 4 are as defined for a compound of formula (I) and R 10 is as defined in 1 ) can be made by reacting a sulfone of formula (9) as defined in 6) first with a base, such as lithium diisopropylamine, potassium ie f-pentoxide or potassium ie f-butoxide, and then with an electrophile, as defined in 9), as shown in Scheme 5.
  • a base such as lithium diisopropylamine, potassium ie f-pentoxide or potassium ie f-butoxide
  • a mono-substituted bicycle of formula (15) as defined in 1 1 ) can be made by reacting a compound of formula (16) as defined in 12) with a base, such as potassium carbonate, in a solvent, such as acetonitrile or /V,/V-dimethylformamide, optionally using microwave heating.
  • a compound of formula (15) can also be prepared in 'one-pot' using conditions described in 12) from a sulfone of formula (9).
  • a sulfone of formula (17) where R 1 , R 2 , R 3a , R 3b and R 4 are as defined for a compound of formula (I) and R 10 is as defined in 1 ) and where R 3a and R 3b are the same as each other, can be made by reacting a sulfone of formula (9) as defined in 6) with typically two equivalents of base and two equivalents of electrophile as defined in 9) in a solvent as defined and described in 12).
  • a sulfone of formula (17) where R 1 , R 2 , R 3a , R 3b and R 4 are as defined for a compound of formula (I) and R 10 is as defined in 1 ) and where R 3a and R 3b are different from each other, can be prepared by reacting a sulfone of formula (16) as defined in 12) with a base such as potassium ie f-pentoxide in a solvent, such as N,N- dimethylformamide, and then with an electrophile as defined in 9).
  • a sulfone of formula (17) can also be prepared by reacting a sulfone of formula (9) as defined in 6) with typically two equivalents of base and successively two different electrophiles, optionally isolating the intermediate.
  • a gem-disubstituted bicycle of formula (14) where R 1 , R 2 , R 3a ,R 3b and R 4 are as defined for a compound of formula (I) can be prepared by reacting a compound of formula (17) as defined in 15) with a base, such as potassium carbonate, in a solvent, such as acetonitrile or /V,/V-dimethylformamide, optionally using microwave heating.
  • a gem-disubstituted bicycle of formula (14) can also be prepared in 'one-pot' using conditions described in 12), 14) and 15) from a sulfone of formula (9).
  • a thioester compound of formula (18) where R 1 and R 2 are as defined for a compound of formula (I) and R 11 is as defined in 1 ) can be made by reacting a carboxylic ester of formula (4) as defined in 2) with potassium thioacetate in a solvent, such as acetone or an alcohol, optionally using microwave heating, as shown in Scheme 6.
  • a thioether of formula (6) where R 1 , R 2 and R 4 are as defined for a compound of formula (I) and R 11 is as defined in 1 ) can be made by reacting a thioester of formula (18) as defined in 17) with a benzylic compound of formula (7) where R 4 is as defined for a compound of formula (I) and LG is a leaving group, for example a halide [such as chloride, bromide or iodide], tosylate, mesylate or triflate, in the presence of a base [such as potassium carbonate] in a solvent [such as acetonitrile, /V,/V-dimethylformamide, methanol or ethanol] and optionally using microwave heating.
  • a halide such as chloride, bromide or iodide
  • a base such as potassium carbonate
  • solvent such as acetonitrile, /V,/V-
  • a thioether of formula (6) as defined in 4) can be made by reacting a carboxylic ester of formula (4) as defined in 2) with a thioester compound of formula (19) where R 4 is as defined for a compound of formula (I), in the presence of a base, such as potassium carbonate, in a solvent, such as acetonitrile, N,N- dimethylformamide or an alcohol, optionally using microwave heating.
  • a base such as potassium carbonate
  • a solvent such as acetonitrile, N,N- dimethylformamide or an alcohol
  • Thioester compounds of formula (19) can be made by reacting a benzylic compound of formula (7) as defined in 4) with potassium thioacetate in a solvent, such as ethanol, tetrahydrofuran, 2-butanone or acetone, optionally using microwave heating.
  • a solvent such as ethanol, tetrahydrofuran, 2-butanone or acetone
  • An allyl ether of formula (21 ) where J is defined as hydrogen, halogen, or haloalkyi and Q is defined as halogen can be prepared by reacting a compound of formula (20) where J and Q are as defined for a compound of formula (21 ) with allyl bromide with a base [such as potassium carbonate] in a solvent [such as acetone or acetonitrile], optionally including a catalyst [such as sodium iodide] and optionally using heating.
  • Phenols of formula (20) are commercially available or can be made by methods known to a person skilled in the art.
  • a phenol of formula (22) where J is defined as hydrogen, halogen, or haloalkyi and Q is defined as halogen can be prepared by heating a compound of formula (21 ) as defined in 20) neat or in a solvent such as /V,/V-dimethylformamide, ⁇ /,/V-dimethylaniline or /V-methyl-2-pyrrolidone.
  • a benzyl ether of formula (23) where J is defined as hydrogen, halogen, or haloalkyi and Q is defined as halogen can be prepared by reacting a phenol of formula (22) as defined in 21 ) with benzyl bromide with a base [such as potassium carbonate] in a solvent [such as acetone or acetonitrile] and optionally using heating.
  • An aldehyde of formula (24) where J is defined as hydrogen, halogen, or haloalkyi and Q is defined as halogen can be prepared by reacting compounds of formula (23) as defined in 22) firstly with ozone [in a solvent such as dichloromethane] then with dimethylsulfide in a 'one pot' procedure.
  • a carboxylic acid of formula (25) where J is defined as hydrogen, halogen, or haloalkyi and Q is defined as halogen can be prepared by reacting aldehydes of formula (24) as defined in 23) with an oxidant [such as sodium chlorite or aqueous hydrogen peroxide or a mixture of both] with potassium phosphate monobasic in a solvent system [such as aqueous ie f-butanol or aqueous acetonitrile] optionally including an alkene [such as 2-methyl-but-2-ene or isobutylene] as an additional reagent.
  • an oxidant such as sodium chlorite or aqueous hydrogen peroxide or a mixture of both
  • potassium phosphate monobasic such as aqueous ie f-butanol or aqueous acetonitrile
  • an alkene such as 2-methyl-but-2-ene or isobutylene
  • a benzylic bromide of formula (7a) where J is defined as hydrogen, halogen, or haloalkyi and Q is defined as halogen can be prepared by reacting carboxylic acids of formula (25) as defined in 24) firstly with oxalyl chloride in a solvent [such as dichloromethane or chloroform] optionally including /V,/V-dimethylformamide as a catalyst then secondly with 2-mercapto-pyridine-1 -/V-oxide sodium salt in bromotrichloromethane as solvent.
  • a solvent such as dichloromethane or chloroform
  • the compounds of Formula (I) according to the invention can be used as herbicides by themselves, but they are generally formulated into herbicidal compositions using formulation adjuvants, such as carriers, solvents and surface-active agents (SFAs).
  • formulation adjuvants such as carriers, solvents and surface-active agents (SFAs).
  • the present invention further provides a herbicidal composition comprising a herbicidal compound according to any one of the previous claims and an agriculturally acceptable formulation adjuvant.
  • the composition can be in the form of concentrates which are diluted prior to use, although ready-to-use compositions can also be made. The final dilution is usually made with water, but can be made instead of, or in addition to, water, with, for example, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
  • the herbicidal compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, compounds of Formula I and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance.
  • compositions can be chosen from a number of formulation types, many of which are known from the Manual on Development and Use of FAO Specifications for Plant Protection Products, 5th Edition, 1999. These include dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO)), micro-emulsions (ME), suspension concentrates (SC), aerosols, capsule suspensions (CS) and seed treatment formulations.
  • the formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of Formula (I).
  • Dustable powders may be prepared by mixing a compound of Formula (I) with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.
  • solid diluents for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers
  • Soluble powders may be prepared by mixing a compound of Formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).
  • water-soluble inorganic salts such as sodium bicarbonate, sodium carbonate or magnesium sulphate
  • water-soluble organic solids such as a polysaccharide
  • WP Wettable powders
  • WG Water dispersible granules
  • Granules may be formed either by granulating a mixture of a compound of Formula (I) and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing a compound of Formula (I) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of Formula (I) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary.
  • a hard core material such as sands, silicates, mineral carbonates, sulphates or phosphates
  • Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils).
  • solvents such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters
  • sticking agents such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils.
  • One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).
  • Dispersible Concentrates may be prepared by dissolving a compound of Formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether. These solutions may contain a surface active agent (for example to improve water dilution or prevent crystallisation in a spray tank).
  • Emulsifiable concentrates or oil-in-water emulsions (EW) may be prepared by dissolving a compound of Formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents).
  • Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N- octylpyrrolidone), dimethyl amides of fatty acids (such as C 8 -Ci 0 fatty acid dimethylamide) and chlorinated hydrocarbons.
  • An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment.
  • Preparation of an EW involves obtaining a compound of Formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion.
  • Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.
  • Microemulsions may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation.
  • a compound of Formula (I) is present initially in either the water or the solvent/SFA blend.
  • Suitable solvents for use in MEs include those hereinbefore described for use in in ECs or in EWs.
  • An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation.
  • An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.
  • SC Suspension concentrates
  • SCs may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of Formula (I).
  • SCs may be prepared by ball or bead milling the solid compound of Formula (I) in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound.
  • One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle.
  • a compound of Formula (I) may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.
  • Aerosol formulations comprise a compound of Formula (I) and a suitable propellant (for example n-butane).
  • a compound of Formula (I) may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as n-propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps.
  • Capsule suspensions may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of Formula (I) and, optionally, a carrier or diluent therefor.
  • the polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure.
  • the compositions may provide for controlled release of the compound of Formula (I) and they may be used for seed treatment.
  • a compound of Formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.
  • the composition may include one or more additives to improve the biological performance of the composition, for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of Formula (I).
  • additives include surface active agents (SFAs), spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of Formula (I)).
  • Wetting agents, dispersing agents and emulsifying agents may be SFAs of the cationic, anionic, amphoteric or non-ionic type.
  • Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltri methyl ammonium bromide), imidazolines and amine salts.
  • Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di- / ' sopropyl- and tri-/ ' sopropyl-naphthalene sulphonates), ether sulphates, alcohol ether sulphates (for example sodium laureth-3-sulphate), ether carboxylates (for example sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (predominately di-esters), for example the reaction between lauryl alcohol and tetra
  • Suitable SFAs of the amphoteric type include betaines, propionates and glycinates.
  • Suitable SFAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); and lecithins.
  • alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof
  • fatty alcohols such as oleyl alcohol or cetyl alcohol
  • alkylphenols such as octylphenol, nonyl
  • Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).
  • hydrophilic colloids such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose
  • swelling clays such as bentonite or attapulgite
  • composition of the present may further comprise at least one additional pesticide.
  • additional pesticide is a herbicide and/or herbicide safener. Examples of such mixtures are (in which T represents a compound of Formula (I)).
  • the mixing partners of the compound of Formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, Fourteenth Edition, British Crop Protection Council, 2006.
  • the compound of Formula (I) can also be used in mixtures with other agrochemicals such as fungicides, nematicides or insecticides, examples of which are given in The Pesticide Manual.
  • the mixing ratio of the compound of Formula (I) to the mixing partner is preferably from 1 : 100 to 1000:1 .
  • mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient” relates to the respective mixture of compound of Formula I with the mixing partner).
  • the compounds of Formula (I) according to the invention can also be used in combination with one or more safeners.
  • mixtures of a compound of Formula I according to the invention with one or more further herbicides can also be used in combination with one or more safeners.
  • the safeners can be AD 67 (MON 4660), benoxacor, cloquintocet-mexyl, cyprosulfamide (CAS RN 221667-31 -8), dichlormid, fenchlorazole-ethyl, fenclorim, fluxofenim, furilazole and the corresponding R isomer, isoxadifen-ethyl, mefenpyr-diethyl, oxabetrinil, N-isopropyl-4-(2-methoxy- benzoylsulfamoyl)-benzamide (CAS RN 221668-34-4).
  • safener compounds disclosed in, for example, EP0365484 e.g N-(2-methoxybenzoyl)-4- [(methylaminocarbonyl)amino]benzenesulfonamide.
  • Particularly preferred are mixtures of a compound of Formula I with cyprosulfamide, isoxadifen-ethyl, cloquintocet-mexyl and/or N- (2-methoxybenzoyl)-4-[(methyl-aminocarbonyl)amino]benzenesulfonamide.
  • the safeners of the compound of Formula I may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 14 th Edition (BCPC), 2006.
  • the reference to cloquintocet-mexyl also applies to a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phos- phonium salt thereof as disclosed in WO 02/34048, and the reference to fenchlorazole- ethyl also applies to fenchlorazole, etc.
  • the mixing ratio of compound of Formula (I) to safener is from 100:1 to 1 :10, especially from 20:1 to 1 :1 .
  • mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient” relates to the respective mixture of compound of Formula I with the safener).
  • the present invention still further provides a method of selectively controlling weeds at a locus comprising crop plants and weeds, wherein the method comprises application to the locus of a weed controlling amount of a composition according to the present invention.
  • Controlling' means killing, reducing or retarding growth or preventing or reducing germination. Generally the plants to be controlled are unwanted plants (weeds). 'Locus' means the area in which the plants are growing or will grow.
  • the rates of application of compounds of Formula (I) may vary within wide limits and depend on the nature of the soil, the method of application (pre- or post-emergence; seed dressing; application to the seed furrow; no tillage application etc.), the crop plant, the weed(s) to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • the compounds of Formula I according to the invention are generally applied at a rate of from 10 to 2000 g/ha, especially from 50 to 1000 g/ha.
  • the application is generally made by spraying the composition, typically by tractor mounted sprayer for large areas, but other methods such as dusting (for powders), drip or drench can also be used.
  • Useful plants in which the composition according to the invention can be used include crops such as cereals, for example barley and wheat, cotton, oilseed rape, sunflower, maize, rice, soybeans, sugar beet, sugar cane and turf.
  • Crop plants can also include trees, such as fruit trees, palm trees, coconut trees or other nuts. Also included are vines such as grapes, fruit bushes, fruit plants and vegetables.
  • Crops are to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO-, ACCase- and HPPD-inhibitors) by conventional methods of breeding or by genetic engineering.
  • herbicides or classes of herbicides e.g. ALS-, GS-, EPSPS-, PPO-, ACCase- and HPPD-inhibitors
  • An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer rape (canola).
  • crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®.
  • the crop plant has been engineered to over-express homogentisate solanesyltrans
  • Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle).
  • Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds).
  • the Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria.
  • Examples of toxins, or transgenic plants able to synthesise such toxins are described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529.
  • transgenic plants comprising one or more genes that code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®.
  • Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding ("stacked" transgenic events).
  • seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate.
  • Crops are also to be understood to include those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).
  • output traits e.g. improved storage stability, higher nutritional value and improved flavour.
  • weeds to be controlled inlcude both monocotyledonous species, for example Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria, Echinochloa, Eleusine, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus, Setaria and Sorghum, and dicotyledonous species, for example Abutilon, Amaranthus, Ambrosia, Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium.
  • monocotyledonous species for example Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria, Echinochloa, Eleusine, Lolium, Monochoria, Rottboellia, Sagittaria,
  • Weeds can also include plants which may be considered crop plants but which are growing outside a crop area ('escapes'), or which grow from seed left over from a previous planting of a different crop ('volunteers'). Such volunteers or escapes may be tolerant to certain other herbicides.
  • 7,7-Dioxo-6-[2-(trifluoromethyl)phenyl]-8H-thiopyrano[3,4-b]pyridin-5-ol (620 mg) was suspended in dichloromethane (20 ml) and treated with pyridine (0.19 ml). Catalytic 4- dimethylaminopyridine (2 mg) was added and the mixture stirred for 5 min. With stirring, isobutyryl chloride (0.21 ml) was added portionwise over 5 min. The reaction was then stirred at ambient temperature for a further 10 min.
  • Table 1 below shows examples of compounds of the invention made in analogous manner to compounds 3.19 and 3.28 described above (see also the general reaction schemes supra).
  • Seeds of a variety of test species are sown in standard soil in pots:- Solanum nigrum (SOLNI), Amaranthus retoflexus (AMARE), Setaria faberi (SETFA), Alopecurus myosuroides (ALOMY), Echinochloa crus-galli (ECHCG), Ipomoea hederacea (IPOHE), Lolium perenne.
  • SOLNI Solanum nigrum
  • AMARE Amaranthus retoflexus
  • SETFA Setaria faberi
  • Alopecurus myosuroides Alopecurus myosuroides
  • Echinochloa crus-galli Echinochloa crus-galli
  • IPHE Ipomoea hederacea

Abstract

L'invention concerne des dérivés de 8H-thiopyrano[3,4-b]pyridine 7,7-dioxyde, des procédés et des intermédiaires pour la préparation de ces composés, des compositions herbicides comprenant ces composés et des procédés d'utilisation de ces composés pour réguler la croissance des plantes.
PCT/EP2015/059615 2014-05-14 2015-05-01 Composés herbicides WO2015173035A1 (fr)

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GBGB1408571.6A GB201408571D0 (en) 2014-05-14 2014-05-14 Herbicidal compounds
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GB201417980A GB201417980D0 (en) 2014-10-10 2014-10-10 Herbicidal compounds

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016174073A1 (fr) * 2015-04-30 2016-11-03 Syngenta Participations Ag Composés herbicides
CN107567455A (zh) * 2015-04-30 2018-01-09 先正达参股股份有限公司 除草化合物
WO2021255091A1 (fr) 2020-06-19 2021-12-23 Bayer Aktiengesellschaft 1,3,4-oxadiazoles et leurs dérivés comme fongicides

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010130970A1 (fr) * 2009-05-14 2010-11-18 Syngenta Limited Composés herbicides
WO2012084755A1 (fr) * 2010-12-23 2012-06-28 Basf Se Pyridines substituées présentant une activité herbicide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010130970A1 (fr) * 2009-05-14 2010-11-18 Syngenta Limited Composés herbicides
WO2012084755A1 (fr) * 2010-12-23 2012-06-28 Basf Se Pyridines substituées présentant une activité herbicide

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016174073A1 (fr) * 2015-04-30 2016-11-03 Syngenta Participations Ag Composés herbicides
KR20170141678A (ko) * 2015-04-30 2017-12-26 신젠타 파티서페이션즈 아게 제초성 화합물
CN107567455A (zh) * 2015-04-30 2018-01-09 先正达参股股份有限公司 除草化合物
US10385063B2 (en) 2015-04-30 2019-08-20 Syngenta Participations Ag Herbicidal compounds
KR102607298B1 (ko) 2015-04-30 2023-11-27 신젠타 파티서페이션즈 아게 제초성 화합물
WO2021255091A1 (fr) 2020-06-19 2021-12-23 Bayer Aktiengesellschaft 1,3,4-oxadiazoles et leurs dérivés comme fongicides

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