NZ623874B2 - Compounds with nematicidal activity - Google Patents

Compounds with nematicidal activity Download PDF

Info

Publication number
NZ623874B2
NZ623874B2 NZ623874A NZ62387412A NZ623874B2 NZ 623874 B2 NZ623874 B2 NZ 623874B2 NZ 623874 A NZ623874 A NZ 623874A NZ 62387412 A NZ62387412 A NZ 62387412A NZ 623874 B2 NZ623874 B2 NZ 623874B2
Authority
NZ
New Zealand
Prior art keywords
alkyl
halogen atoms
halogenoalkyl
alkoxy
phenyl
Prior art date
Application number
NZ623874A
Other versions
NZ623874A (en
Inventor
Lionel Carles
Pierre Yves Coqueron
Philippe Desbordes
Martin Fusslein
Ulrich Gorgens
Jorg Nico Greul
Kerstin Ilg
Kristian Kather
Peter Losel
Olga Malsam
Original Assignee
Bayer Animal Health Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from EP11187507.6A external-priority patent/EP2589292A1/en
Priority claimed from EP11194886.5A external-priority patent/EP2606728A1/en
Application filed by Bayer Animal Health Gmbh filed Critical Bayer Animal Health Gmbh
Priority claimed from PCT/EP2012/071385 external-priority patent/WO2013064460A1/en
Publication of NZ623874A publication Critical patent/NZ623874A/en
Publication of NZ623874B2 publication Critical patent/NZ623874B2/en

Links

Classifications

    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/40—Acylated substituent nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/61—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6

Abstract

The disclosure relates to pyridyl carboxamide derivatives of general formula (I), wherein B can be 2-pyridyl, 3-pyridyl or 4-pyridyl and the other moieties are as disclosed in the specification. These compounds are used as nematicides the disclosure also relates to methods for the control of nematodes. Example compounds include: 2-[4-chloro-6-(trifluoromethyl)pyridin-3-yl]ethanamine 3-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]butan-2-amine 3-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]butan-2-one 2- [3 -chloro-5-(trifluoromethyl)pyridin-2-yl]-1-{[2-(trifluoromethyl)benzoyl] amino}ethyl acetate N-{2-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]-2-methylpropyl} -2-(trifluoromethyl)benzamide es. Example compounds include: 2-[4-chloro-6-(trifluoromethyl)pyridin-3-yl]ethanamine 3-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]butan-2-amine 3-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]butan-2-one 2- [3 -chloro-5-(trifluoromethyl)pyridin-2-yl]-1-{[2-(trifluoromethyl)benzoyl] amino}ethyl acetate N-{2-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]-2-methylpropyl} -2-(trifluoromethyl)benzamide

Description

/071385 Compounds with nematicidal activity The present invention relates to the use of predominantly known pyridyl carboxamide derivatives as nematicides, compositions containing such compounds and methods for the l of nematodes.
Nematodes cause a substantial loss in agricultural product including food and rial crops and are combated with chemical compounds having nematicidal activity. To be useful in agriculture these compounds should have a high ty, a broad spectrum activity against ent strains of nematodes and should not be toxic to non—target organisms.
The use of certain N—2-(pyridyl)ethyl-carboxamide derivatives for controlling nematodes is bed in EP 2132 987 A1.
Most of the compounds of formula (I) described below are known from A1 (later, e.g. in the Tables, referred to as P1), WO 2005/058828 A1 (P2), /014545 A2 (P3), WO 2005/103004 A1 (P4), A1 (P5), EP 2 289 880 A1 (P6), A1 (P7) and WO 08192 A1 (P8). There it is stated that they can be used as fungicides. ly WC 2012/1 18139 was published. It discloses compounds with nematicidal activity.
Surprisingly it has now been found that these compounds exhibit nematicidal activity and can therefore be used to control nematodes.
It was also found that the compounds of formula (1) exhibit ty against bacteria and viruses and can be used as bactericides and as virucides.
Accordingly, the present invention relates to the use of a compound of formula (1) B R31 xx 9% A R R R5 wherein B ents 2-pyridyl, dyl, or 4-pyridyl, X is selected from the group consisting of halogen, nitro, cyano, hydroxy, amino, —SH, —SF5, —CHO, — OCHO, —NHCHO, —COOH, —CONH2, —CONH(OH), —OCONH2, (hydroxyimino)—C1-C6-alkyl, C1- Cg-alkyl, C1-Cg-halogenoalkyl having lto 5 halogen atoms, C2-Cg-alkenyl, C2-Cg-alkynyl, C1-C3- alkylamino, di-(Cl-Cg-alkyl)amino, C1-Cg-alkoxy, C1-Cg-halogenoalkoxy having 1 to 5 halogen atoms,, C2-Cg-alkenyloxy, C2-Cg-halogenoalkenyloxy having 1 to 5 halogen atoms, C3-C3- alkynyloxy, C3-Cg-halogenoalkynyloxy having 1 to 5 halogen atoms, C3-Cg-cycloalkyl, C3-C3- _ 2 _ nocycloalkyl having 1 to 5 halogen atoms, C1-Cg-alkylcarbonyl, C1-C3- halogenoalkylcarbonyl having 1 to 5 halogen atoms, -CONH(C1-Cg-alkyl), -CON(C1-Cg-alkyl)2, - CONH(OC1-Cg-alkyl), C1-Cg-alkyl)(C1-Cg-alkyl), C1-Cg-alkoxycarbonyl, C1-C3- halogenoalkoxycarbonyl having 1 to 5 halogen atoms, C1-Cg-alkylcarbonyloxy, C1-C3- halogenoalkylcarbonyloxy having 1 to 5 halogen atoms, alkylcarbonylamino, C1-C3- halogenoalkylcarbonylamino having lto 5 halogen atoms, (C1-Cg-alkyl), -OCON(C1-Cg- 2, —OCONH(OC1—Cg—alkyl), —OCO(OC1—Cg—alkyl), —S—C1—Cg—alkyl, —S—C1—Cg—halogenoalkyl having 1 to 5 halogen atoms, —S(O)—C1—Cg—alkyl, —S(O)—C1—Cg—halogenoalkyl having lto 5 halogen atoms, —S(O)2-C1-Cg—alkyl, —S(O)2—C1—Cg—halogenoalkyl having 1 to 5 n atoms, (C1—C6— alkoxyimino)-C1-C6-alkyl, (Cg-Ca-alkenyloxyimino)-C1-C6-alkyl, (C3-C6-alkynyloxyimino)-C1-C6- alkyl, (benzyloxyimino)-C1-C6-alkyl, benzyloxy, -S-benzyl, amino, phenoxy, -S-phenyl and amino, n is 1, 2, 3 or 4 and if n is 2, 3, or 4 then the substituents X may be the same or different, R1 and R2 are the same or different and are selected from the group consisting of hydrogen, halogen, l5 cyano, hydroxy, amino, -SH, -CHO, -OCHO, -NHCHO, -COOH, -CONH2, -CONH(OH), - OCONHZ, (hydroxyimino)-C1-C6-alkyl group, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6- alkylamino, di-(Cl-Ca-alkyl)amino, C1-C6-alkoxy, C1-C6-halogenoalkyl having 1 to 5 halogen atoms, C1-C6-halogenoalkoxy having 1 to 5 halogen atoms, C2-C6-alkenyloxy, C2-C6- halogenoalkenyloxy having 1 to 5 halogen atoms, C3-C6-alkynyloxy, C3-C6-halogenoalkynyloxy having 1 to 5 halogen atoms, C3-C6-cycloalkyl, halogenocycloalkyl having 1 to 5 halogen atoms, C3-C6-Cycloalkyl-C1-C6-alkyl, C3-C5-halogenocycloalkyl-C1-C6-alkyl having 1 to 5 n atoms, C1-C6-alkylcarbonyl, C1-C6-halogenoalkylcarbonyl having 1 to 5 halogen atoms, - CONH(C1-C5-alkyl), -CON(C1-C5-alkyl)2, -CONH(OC1-C5-alkyl), -CON(OCi-Cg-alkyl)(C1-C5- alkyl), C1-C5-alkoxycarbonyl, a C1-C5-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, - OC(O)—C1-C6-alkyl, -OC(O)-C1-C5-halogenoalkyl having 1 to 5 halogen atoms, )-C1-C6- alkyl, -NHC(O)-C1-C6-halogenoalkyl having 1 to 5 halogen atoms, -OCONH(C1-C6-alkyl), - OCON(C1-C6-alkyl)2, -OCONH(OC1-C6-alkyl), OCO(OC1-C6-alkyl), -S-C1-C6-alkyl, -S-C1'C6' halogenoalkyl having 1 to 5 halogen atoms, -S(O)-C1-C6-alkyl, -S(O)-C1-C5-halogenoalkyl having 1 to 5 halogen atoms, -S(O)2-C1-C6-alkyl, -S(O)2-C1-C6-halogenoalkyl having lto 5 halogen atoms, benzyl, benzyloxy, zyl, -S(O)-benzyl, -S(O)2—benzyl, benzylamino, phenoxy, -S-phenyl, - S(O)-phenyl, -S(O)2—phenyl, phenylamino, phenylcarbonylamino, 2,6-dichlorophenylcarbonylamino , 2-chlorophenyl-carbonylamino and phenyl or R1 and R2 together with the carbon atom to which they are bonded form a 3-, 4-, 5- or 6-membered carbocycle, _ 3 _ R3 and R4 are the same or different and are selected from the group consisting of hydrogen, halogen, cyano, hydroxy, amino, -SH, -CHO, -COOH, , -CONH(OH), -OCONH2, (hydroxyimino)-C1-C6-alkyl, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkylamino, di- (C1-C5-alkyl)amino, C1-C6-alkoxy, hydroxy-Cl-Ca-alkyl, C1-C5-alkoxy-C1-C5-alkyl, C1-C6- halogenoalkyl having 1 to 5 n atoms, C1-C5-halogenoalkoxy having 1 to 5 halogen atoms, C2-C6-alkenyloxy, C2-C6-halogenoalkenyloxy having 1 to 5 n atoms, C3-C6-alkynyloxy, C3- C6—halogenoalkynyloxy having 1 to 5 n atoms, C3—C6—cycloalkyl, C3—C5—halogenocycloalkyl having 1 to 5 halogen atoms, C1—C6—alkylcarbonyl, C1—C6—halogenoalkylcarbonyl having 1 to 5 halogen atoms, —CONH(C1—C6—alkyl), —CON(C1—C6—alkyl)2, —CONH(OC1—C6—alkyl), C1— C6-alkyl)(C1-C6-alkyl), C1-C5-alkoxycarbonyl, C1-C6-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, -OC(O)-C1-C6-alkyl, -OC(O)-C1-C6-halogenoalkyl having 1 to 5 halogen atoms, - NHC(O)-C1-C6-alkyl, -NHC(O)-C1-C6-halogenoalkyl having 1 to 5 halogen atoms, -OCONH(C1- Cs-alkyl), -OCON(C1-C6-alkyl)2, (OC1-C6-alkyl), OCO(OC1-C6-alkyl), -S-C1-C6-alkyl, - S-C1-C6-halogenoalkyl having 1 to 5 halogen atoms, -S(O)-C1-C6-alkyl, -S(O)-C1-C6- halogenoalkyl having 1 to 5 halogen atoms, -S(O)2-C1-C6-alkyl, -S(O)2-C1-C6-halogenoalkyl having 1 to 5 n atoms, benzyl, benzyloxy, -S-benzyl, -S(O)—benzyl, -S(O)2-benzyl, benzylamino, y, -S-phenyl, -S(O)-phenyl, -S(O)2-phenyl, phenylamino, carbonylamino, 2-chlorophenyl-carbonylamino, 2,6-dichlorophenyl-carbonylamino and phenyl; R5 is selected from the group consisting of hydrogen, cyano, -CHO, -OH, C1-C6-alkyl, C1-C6- halogenoalkyl having 1 to 5 halogen atoms, C1-C5-alkoxy, C1-C6-halogenoalkoxy having 1 to 5 halogen atoms, C3—C7—cycloalkyl, C3—C7—halogenocycloalkyl having 1 to 5 halogen atoms, C2—C6— alkenyl, C2—C5—alkynyl, C1—C6—alkoxy—C1—C6—alkyl, cycloalkyl—C1—C6—alkyl, cyano—C1—C6— alkyl, amino—Cl—Ca—alkyl, C1—C6—alkylamino—C1—C6—alkyl, di—(C1—C6—alkyl)amino—C1—C6—alkyl, C1— C6-alkylcarbonyl, halogenoalkylcarbonyl having 1 to 5 halogen atoms, C1-C6- alkoxycarbonyl, benzyloxycarbonyl, C1-C6-alkoxy-C1-C6-alkylcarbonyl, -S(O)2-C1-C5-alkyl, and — S(O)2-C1-C6-halogenoalkyl having 1 to 5 halogen atoms; A represents a phenyl group of formula (Al) (A1) Wherein R is selected from the group consisting of halogen, nitro, -OH, NH2, SH, SFs, CHO, OCHO, NHCHO, COOH, cyano, C1-Cg-alkyl, C1-Cg-halogenoalkyl having 1 to 5 halogen atoms, C2-C3- l, C2-Cg-alkynyl, C3-C5-cycloalkyl, -S-C1-Cg-alkyl, -S-C1-Cg-halogenoalkyl having 1 to 5 halogen atoms, C1-Cg-alkoxy, C1-Cg-halogenoalkoxy having 1 to 5 halogen atoms, C1-Cg-alkoxy- C2-Cg-alkenyl, C1-Cg-alkoxycarbonyl, C1-Cg-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, ‐ 4 wed by 4A) ‐ In an aspect, the present invention relates to compounds of formula 3 R3 R4 O Xn 6 6 N N 5 F F R R5 m 2 4 ‐ 4A wed by 4B) ‐ wherein X is selected from the group consisting of halogen, nitro, cyano, hydroxy, amino, - SH, -SF5, -CHO, -OCHO, -NHCHO, -COOH, -CONH2, -CONH(OH), -OCONH2, (hydroxyimino)-C1-C6-alkyl, C1-C8-alkyl, C1-C8-halogenoalkyl having l to 5 n atoms, C2-C8-alkenyl, C2-C8-alkynyl, C1-C8-alkylamino, di-(C1-C8)- alkylamino, alkoxy, C1-C8-halogenoalkoxy having l to 5 halogen atoms, C2- C8-alkenyloxy, C2-C8-halogenoalkenyloxy having l to 5 halogen atoms, C3-C8- alkynyloxy, C3-C8-halogenoalkynyloxy having l to 5 halogen atoms, C3-C8- cycloalkyl, C3-C8-halogenocycloalkyl having l to 5 halogen atoms, C1-C8- alkylcarbonyl, C1-C8-halogenoalkylcarbonyl having l to 5 halogen atoms, - CONH(C1-C8-alkyl), 1-C8-alkyl)2, -CONH(OC1-C8-alkyl), -CON(OC1-C8- alkyl)(C1-C8-alkyl), C1-C8-alkoxycarbonyl, halogenoalkoxycarbonyl having l to 5 halogen atoms, C1-C8-alkylcarbonyloxy, C1-C8-halogenoalkylcarbonyloxy having 1 to 5 halogen atoms, C1-C8-alkylcarbonylamino, C1-C8- halogenoalkylcarbonylamino having l to 5 halogen atoms, -OCONH(C1-C8-alkyl), -OCON(C1-C8-alkyl)2, -OCONH(OC1-C8-alkyl), -OCO(OC1-C8-alkyl), -S-C1-C8- alkyl, -S-C1-C8-halogenoalkyl having l to 5 halogen atoms, -S(O)-C1-C8-alkyl, - S(O)-C1-C8-halogenoalkyl having l to 5 halogen atoms, -S(O)2-C1-C8-alkyl, -S(O)2- C1-C8-halogenoalkyl having l to 5 halogen atoms, (C1-C6-alkoxyimino)-C1-C6- alkyl, (C2-C6-alkenyloxyimino)-C1-C6-alkyl, (C3-C6-alkynyloxyimino)-C1-C6- alkyl, (benzyloxyimino)-C1-C6-alkyl, benzyloxy, -S-benzyl, benzylamino, y, -S-phenyl and phenylamino, n is 1, 2, 3 or 4 and if n is 2, 3, or 4 then the substituents X may be the same or different, R3 and R4 are the same or different and are ed from the group consisting of hydrogen, halogen, cyano, y, amino, -SH, -CHO, -COOH, -CONH2, - CONH(OH), -OCONH2, (hydroxyimino)-C1-C6-alkyl, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkylamino, di-(C1-C6-alkyl)amino, C1-C6-alkoxy, hydroxy- C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-halogenoalkyl having 1 to 5 halogen atoms, C1-C6-halogenoalkoxy having 1 to 5 n atoms, C2-C6-alkenyloxy, C2- C6-halogenoalkenyloxy having 1 to 5 halogen atoms, C3-C6-alkynyloxy, C3-C6- halogenoalkynyloxy having 1 to 5 n atoms, C3-C6-cycloalkyl, C3-C6- ‐ 4B (followed by 4C) ‐ nocycloalkyl having 1 to 5 halogen atoms, C1-C6-alkylcarbonyl, C1-C6- halogenoalkylcarbonyl having 1 to 5 halogen atoms, -CONH(C1-C6-alkyl), - -C6-alkyl)2, -CONH(OC1-C6-alkyl), -CON(OC1-C6-alkyl)(C1-C6-alkyl), C1-C6-alkoxycarbonyl, C1-C6-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, -OC(O)-C1-C6-alkyl, -OC(O)-C1-C6-halogenoalkyl having 1 to 5 halogen atoms, -NHC(O)-C1-C6-alkyl, -NHC(O)-C1-C6-halogenoalkyl having 1 to 5 n atoms, -OCONH(C1-C6-alkyl), -OCON(C1-C6-alkyl)2, -OCONH(OC1-C6- alkyl), OCO(OC1-C6-alkyl), -S-C1-C6-alkyl, -S-C1-C6-halogenoalkyl having 1 to 5 halogen atoms, -S(O)-C1-C6-alkyl, -S(O)-C1-C6-halogenoalkyl having 1 to 5 halogen atoms, -S(O)2-C1-C6-alkyl, -S(O)2-C1-C6-halogenoalkyl having 1 to 5 halogen atoms, benzyl, benzyloxy, -S-benzyl, benzyl, -S(O)2-benzyl, benzylamino, phenoxy, -S-phenyl, -S(O)-phenyl, -S(O)2-phenyl, phenylamino, phenylcarbonylamino, 2-chlorophenyl-carbonylamino, chlorophenylcarbonylamino and phenyl; R5 is selected from the group consisting of hydrogen, cyano, -CHO, -OH, C1-C6-alkyl, C1-C6-halogenoalkyl having 1 to 5 halogen atoms, C1-C6-alkoxy, C1-C6- halogenoalkoxy having 1 to 5 halogen atoms, C3-C7-cycloalkyl, C3-C7- halogenocycloalkyl having 1 to 5 halogen atoms, C2-C6-alkenyl, C2-C6-alkynyl, C1- C6-alkoxy-C1-C6-alkyl, C3-C7-cycloalkyl-C1-C6-alkyl, cyano-C1-C6-alkyl, amino- C1-C6-alkyl, C1-C6-alkylamino-C1-C6-alkyl, di-C1-C6-alkylamino-C1-C6-alkyl, C1- C6-alkylcarbonyl, C1-C6-halogenoalkylcarbonyl having 1 to 5 halogen atoms, C1- C6-alkoxycarbonyl, benzyloxycarbonyl, C1-C6-alkoxy-C1-C6-alkylcarbonyl, - S(O)2-C1-C6-alkyl, and –S(O)2-C1-C6-halogenoalkyl having 1 to 5 halogen atoms; R is selected from the group consisting of halogen, nitro, -OH, NH2, SH, SF5, CHO, OCHO, NHCHO, COOH, cyano, C1-C8-alkyl, C1-C8-halogenoalkyl having 1 to 5 halogen atoms, C2-C8-alkenyl, C2-C8-alkynyl, C3-C6-cycloalkyl, -S-C1-C8-alkyl, - S-C1-C8-halogenoalkyl having 1 to 5 n atoms, alkoxy, C1-C8- halogenoalkoxy having 1 to 5 n atoms, C1-C8-alkoxy-C2-C8-alkenyl, C1-C8- alkoxycarbonyl, C1-C8-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, C1- C8-alkylcarbonyloxy, C1-C8-halogenoalkylcarbonyloxy having 1 to 5 halogen atoms, -S(O)-C1-C8-alkyl, -S(O)-C1-C8-halogenoalkyl having 1 to 5 halogen atoms, -S(O)2-C1-C8-alkyl, -S(O)2-C1-C8-halogenoalkyl having 1 to 5 halogen atoms, C1- ‐ 4C (followed by 4D) ‐ C8-alkylsulfonamide, -NH(C1-C8-alkyl), N(C1-C8-alkyl)2, phenyl (optionally substituted by alkoxy) and phenoxy, or two R bonded to adjacent carbon atoms er represent –O(CH2)pO-, wherein p represents 1 or 2, m is 0, 1, 2, 3, 4 or 5 and if m is 2, 3, 4, or 5 then the substituents R may be the same or different.
In another , the present invention relates to compounds of a CF Cl R3 R4 6 N N F F R5 . in which R3, R4 and R5 have the meanings as described herein.
In another aspect, the present invention relates to compounds of formula CF Cl 6 N N F F H .
In another aspect, the present invention relates to compounds of formula Cl Cl R3 R4 6 N N F F R5 . in which R3, R4 and R5 have the meanings as described herein. ‐ 4D (followed by 5) ‐ In another aspect, the present invention relates to a compound of formula Cl Cl 6 N N F F H .
In a particular embodiment, the present invention s to a use of compounds as described herein for controlling plant nematodes. _ 5 _ The ion also relates to the use of salts, N-oxides, metal complexes and metalloid complexes of nds of formula (1) against nematodes.
A preferred embodiment of the present invention is the use of compounds of formula (la) (la) wherein R, R1, R2, R3, R4, R5 X, n, and m have the meanings given above, for the control of nematodes.
Another preferred embodiment of the present invention is the use of compounds of formula (1b) wherein R, R1, R2, R3, R4, R5 X, n, and m have the meanings given above, for the control of nematodes.
Another preferred embodiment of the present invention are compounds of formula (Ib-al) (lb-a1) wherein R, R1, R2, R3, R4, R5, n and m have the meanings given above and X represents halogen. ably n represents 3 in which case the halogen-atoms (in particular chloro-atoms) are in the 2- and 4-position.
Another preferred embodiment of the present invention are compounds of formula (Ib-aZ) wherein R, R1, R2, R3, R4, R5, n and 111 have the meanings given above and X represents halogen.
Preferably n ents 3 in which case the n-atoms (in particular -atoms) are in the 2- and 4-position. _ 6 _ Another preferred embodiment of the present invention is the use of compounds of a (1c) wherein R, R1, R2, R3, R4, R5 X, n, and m have the meanings given above, for the control of nematodes.
Other preferred embodiments of the present invention are compounds of formula (I), (la), (1b), (lb-a1), (Ib-a2) and (1c) in which R1 and R2 both represent halogen and in particular R1 and R2 both represent Compounds of formula (1) can for e be prepared by reacting a compound of formula (II) R R / / H Xn 3% 1 2 [T] R R R5 (11) wherein X, n, R1, R2, R3, R4, and R5 are defined as above, with a compound of formula (111) '- A (111) wherein A is defined as above, and L is a leaving group selected from the group consisting of halogen, hydroxyl, optionally substituted alkyl, ally substituted benzyl and a group of formula 0 A usually in the presence of a base, a condensing agent and in the presence of a solvent.
This process and other processes for the ation of the compounds of formula (I) as well as intermediates for the preparation of compounds of formula (I) are described in more detail in WO 2001/011965 A1 (P1), A1 (P2), W02005/014545 A2 (P3), A1 (P4), A1 (P5), EP 2 289 880 A1 (P6), A1 (P7), A1 (P8), WO 74280 A1 (P9), A2 (P10), A1 (P11), WO 03006 A1 (P12), A1 (P13), A1 (P14), A1 (P15) and A2 (P16).
In compounds of formula (I), the use of which is preferred, R, R1, R2, R3, R4, R5 X, B, n and m have the following meanings. _ 7 _ B represents 2-pyridyl, 3-pyridyl, or 4-pyridyl.
X is ed from the group consisting of halogen, nitro, cyano, C1-C4-alkyl, C1-C4-halogenoalkyl having 1 to 5 halogen atoms, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkylamino, di-(Cl-C4- alkyl)amino, C1-C4-alkoxy, C1-C4-halogenoalkoxy having 1 to 5 halogen atoms, C2-C4-alkenyloxy, C2-C4-halogenoalkenyloxy having 1 to 5 halogen atoms, C3-C4-alkynyloxy, C3-C4- halogenoalkynyloxy having 1 to 5 halogen atoms, C3-C6-cycloalkyl, C3-C5-halogenocycloalkyl having 1 to 5 n atoms, C1-C4-alkylcarbonyl, C1-C4-halogenoalkylcarbonyl having 1 to 5 halogen atoms, -CONH(C1-C4-alkyl), -CON(C1-C4-alkyl)2, -CONH(OC1-C4-alkyl), -CON(OC1- C4-alkyl)(C1-C4-alkyl), C1-C4-alkoxycarbonyl, C1-C4-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, C1-C4-alkylcarbonyloxy, C1-C4-halogenoalkylcarbonyloxy having 1 to 5 halogen atoms, C1-C4-alkylcarbonylamino, C1-C4-halogenoalkylcarbonylamino having 1 to 5 halogen atoms, -OCONH(C1-C4-alkyl), C1-C4-alkyl)2, -OCONH(OC1-C4-alkyl), -OCO(OC1-C4- alkyl), -S-C1-C4-alkyl, -S-C1-C4-halogenoalkyl having lto 5 halogen atoms, -S(O)-C1-C4-alkyl, - S(O)—C1-C4-halogenoalkyl having 1 to 5 halogen atoms, -S(O)2-C1-C4-alkyl, -S(O)2-C1-C4- halogenoalkyl having 1 to 5 halogen atoms, (C1-C4-alkoxyimino)-C1-C4-alkyl, (C2-C6- loxyimino)-C1-C4-alkyl, (C3-C6-alkynyloxyimino)-C1-C4-alkyl, loxyimino)-C1-C6- alkyl, benzyloxy, -S-benzyl, amino, phenoxy, -S-phenyl and phenylamino, n is 1, 2, 3 or 4 and ifn is 2, 3, or 4 then the substituents X may be the same or different.
R1 and R2 are the same or ent and are selected from the group consisting of hydrogen, halogen, cyano, hydroxy, amino, -CHO, -OCHO, -NHCHO, -COOH, -CONH2, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkylamino, di-(Cl-C4-alkyl)amino, C1-C4-alkoxy, halogenoalkyl having 1 to 5 halogen atoms, C1—C4—halogenoalkoxy having 1 to 5 halogen atoms, C2—C4— alkenyloxy, halogenoalkenyloxy having 1 to 5 n atoms, C3—C4—alkynyloxy, C3—C4— halogenoalkynyloxy having 1 to 5 halogen atoms, C3—C6—cycloalkyl, halogenocycloalkyl having 1 to 5 halogen atoms, cycloalkyl-C1-C3-alkyl, C3-C6-halogenocycloalkyl-C1-C3-alkyl having 1 to 5 halogen atoms, C1-C4-alkylcarbonyl, C1-C4-halogenoalkylcarbonyl having 1 to 5 halogen atoms, -CONH(C1-C4-alkyl), -CON(C1-C4-alkyl)2, -CONH(OC1-C4-alkyl), -CON(OC1- C4-alkyl)(C1-C4-alkyl), C1-C4-alkoxycarbonyl, C1-C4-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, -C1-C4-alkyl, -OC(O)-C1-C4-halogenoalkyl having 1 to 5 halogen atoms, - NHC(O)-C1-C4-alkyl, -NHC(O)-C1-C4-halogenoalkyl having 1 to 5 halogen atoms, -OCONH(C1- C4-alkyl), -OCON(C1-C4-alkyl)2, -OCONH(OC1-C4-alkyl), OCO(OC1-C4-alkyl), -S-C1-C4-alkyl, - S-Cl-C4-halogenoalkyl having 1 to 5 halogen atoms, -S(O)-C1-C4-alkyl, -S(O)-C1-C4- halogenoalkyl having 1 to 5 halogen atoms, -C1-C4-alkyl, -S(O)2-C1-C4-halogenoalkyl having 1 to 5 halogen atoms, benzyl, benzyloxy, -S-benzyl, -S(O)-benzyl, -S(O)2—benzyl, benzylamino, phenoxy, -S-phenyl, -S(O)-phenyl, -S(O)2—phenyl, phenylamino, _ 8 _ phenylcarbonylamino, chlorophenyl-carbonylamino, 2-chlorophenyl-carbonylamino and phenyl or R1 and R2 together with the carbon atom to which they are bonded form a 3-, 5- or 6-membered carbocycle, R3 and R4 are the same or different and are selected from the group ting of en, halogen, cyano, hydroxy, amino, -CHO, -COOH, -CONH2, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1- C4—alkylamino, di—(Cl—C4—alkyl)amino, C1—C4—alkoxy, hydroxy—C1—C4—alkyl, C1—C4—alkoxy—C1—C3— alkyl, C1—C4—halogenoalkyl having 1 to 5 halogen atoms, C1—C4—halogenoalkoxy having 1 to 5 halogen atoms, C2—C4—alkenyloxy, halogenoalkenyloxy having 1 to 5 halogen atoms, C3—C4— alkynyloxy, C3-C4-halogenoalkynyloxy having 1 to 5 halogen atoms, C3-C6-cycloalkyl, C3-C6- halogenocycloalkyl having 1 to 5 halogen atoms, C1-C4-alkylcarbonyl, C1-Cz- halogenoalkylcarbonyl having 1 to 5 halogen atoms, -CONH(C1-C4-alkyl), -CON(C1-C4-alkyl)2, - CONH(OC1-C4-alkyl), C1-C4-alkyl)(C1-C4-alkyl), alkoxycarbonyl, C1-Cz- halogenoalkoxycarbonyl having 1 to 5 halogen atoms, -OC(O)-C1-C4-alkyl, -OC(O)-C1-Cz- halogenoalkyl having 1 to 5 halogen atoms, -NHC(O)-C1-C4-alkyl, -NHC(O)-C1-C4-halogenoalkyl having 1 to 5 halogen atoms, -OCONH(C1-C4-alkyl), -OCON(C1-C4-alkyl)2, -OCONH(OC1-Cz- , OCO(OC1-C4-all In compounds of formula (I), the use of which is particularly preferred, R, R1, R2, R3, R4, R5 X, B, n and m have the following meanings.
B represents 2-pyridyl, 3-pyridyl, or 4-pyridyl.
X is selected from the group consisting of halogen,, C1-C4-alkyl, halogenoalkyl having lto 5 halogen atoms, C1-C4-alkoxy. 1’1 is l, 2, 3 or 4 and if n is 2, 3, or 4 then the tuents X may be the same or different.
R1 and R2 are the same or different and are selected from the group consisting of hydrogen, halogen, cyano, hydroxy, C1-C4-alkyl, alkenyl, C2-C4-alkynyl, C1-C4-alkoxy, C3-C6-cycloalkyl-C1- Cg-alkyl, C1-C4-alkoxycarbonyl, -OC(O)-C1-C4-alkyl, -NHC(O)-C1-C4-alkyl, 2,6-dichlorophenylcarbonylamino , 2-chlorophenyl-carbonylamino and phenyl or R1 and R2 together with the carbon atom to which they are bonded form a 3-or 5-membered carbocycle.
R3 and R4 are the same or different and are selected from the group ting of hydrogen, -COOH, C1- C4-alkyl, C1-C4-halogenoalkyl C1-C4-alkoxy, hydroxy—Ci-C4-alkyl, alkoxy-Ci-C3-alkyl, - CONH(C1-C4-alkyl), C1-C4-alkoxycarbonyl, -OC(O)-C1-C4-alkyl, and phenyl. is selected from the group consisting of hydrogen, C3-C6-cycloalkyl, C1-C4-alkylcarbonyl, and C1- C4-alkoxycarbonyl.
A represents a phenyl group of formula (Al) (A1) _ 10 _ R is selected from the group consisting of halogen, nitro, -OH, cyano, C1-C4-alkyl, C1-C4- halogenoalkyl having 1 to 5 halogen atoms, C3-C6-cycloalkyl, C1-C4-alkoxy, C1C1-C4- alkoxycarbonyl, -NH(C1-C4-alkyl), phenyl (optionally substituted by C1-C4-alkoxy) and phenoxy. m is 0, 1, 2 or3 and ifm is 2 or 3 then the substituents R may be the same or different.
The provisos mentioned above apply also With regard to the red and particularly preferred definitions.
A "nematicide" as used herein means that the compound is capable of controlling nematodes.
"Controlling nematodes" as used in the present ion means killing nematodes or preventing nematodes to develop or to grow. Controlling nematodes as used herein also encompasses controlling nematode progeny (development of viable cysts and/or egg masses). The compounds described herein, may be used to keep an organism healthy and may be used curatively, pre-emptively or systematically to control nematodes.
The "organism" as mentioned in the above paragraphs may be a plant. When using the compounds bed , to keep a plant healthy, the controlling of nematodes as used herein asses the reduction of damage to plants and/or encompasses sed yield.
Altematively, the organisms as mentioned above may be a human or an animal. When using the compounds described herein to keep a human or animal healthy, the use encompasses therapeutic use and narian use with the aim to prevent or to cure damage by nematodes.
"Nematodes" as used herein encompass all species of the order Nematoda and in particular species that are parasitic or cause health problems to plants or to fungi (for example species of the orders Aphelenchida, ogyne, Tylenchida and others) or to humans and animals (for example species of the orders Ascaradida, Oxyurida, Strongylida, Stronglyloides and Trichocephalida). ably, "nematodes" as used herein, refer to plant nematodes meaning plant tic nematodes that cause damage to plants. Plant nematodes encompass plant parasitic nematodes and nematodes living in the soil. Plant parasitic nematodes include, but are not limited to, ectoparasites such as Xiphinema Spp., Longidorus Spp., and Trichodorus Spp.; semiparasites such as Tylenchulus Spp.; migratory endoparasites such as enchus Spp., Radopholus spp., and Scutellonema Spp.; sedentary parasites such as Heterodera Spp., Globodeml 51717., and Meloidogyne Spp., and stem and leaf endoparasites such as Dilylenchus spp., Aphelenchoides spp., and Hirshmaniella spp.. The compounds described herein are distinguished ally for their effective l of halmful root parasitic soil nematodes such as, rming nematodes of the genera Heterodem or Globodem, and/or root knot nematodes of the genus _ 11 _ Meloidogyne. Harmful species of these genera are for example Meloidogyne incognata, dera glycines (soybean cyst nematode), Globodera pallida and Globodera rostochiensis (potato cyst nematode), Which species are effectively controlled With the compounds described herein. However, the use of the compounds described herein is in no way restricted to these genera or species, but also extends in the same manner to other des.
The compounds described herein may have a broad spectrum activity against various genera and/or strains and/or species of nematodes including but not limited to e. g. Aglenchus agricola, Anguina tritici, Aphelenchoides arachz'dis, Aphelenchoidesfragaria and the stem and leaf endoparasites Aphelenchoides spp. in l, Belonolaz’mus z's, Belonolaimus longicaudatus, Belonolaimus nortom', Bursaphelenchus eremuS, Bursaphelenchus xylophilus and Bursaphelenchus Spp. in general, Cacapaurus pestis, Criconemella curvata, Criconemella onoensis, Criconemella ornata, Criconemella rusium, Criconemella xenoplax (= Mesocriconema ax) and Criconemella spp. in general, Criconemoides ferm'ae, Criconemoides onoense, Criconemoides amatum and Criconemoides Spp. in general, Dilylerzchus destructor, Dilylenchus dipsaci, Dilylenchus myceliophagus and the stem and leaf endoparasites Dilylenchus spp. in general, Dolichodoms heterocephalus, Globodera pallida (=Heterodera pallida), Globodem rostochiensis o cyst nematode), Globodera cearum, Globodera tabacum, Globodera Virginia and the sedentary, cyst forming parasites Globodera Spp. in general,, Helicolylenchus digonicus, lylenchus dihystera, Helicolylenchus erythrine, Helicolylenchus multicinctus, Helicolylenchus nannus, Helicolylenchus pseudorobustus and Helicolylenchus Spp. in l, Hemicriconemoides, cliophom arenaria, Hemicycliophom nudata, cliophora parvana, Heterodera avenae, Heterodera erae, Heterodem glycines (soybean cyst nematode), Heterodera oryzae, Heterodera schachtii, Heterodem zeae and the sedentary, cyst forming parasites Heterodem Spp. in general, Hirschmaniella gracilz's, Hirschmaniella oryzae Hirschmaniella spinicaudata and the stem and leaf rasites Hirschmaniella spp. in general, Hoplolaz'mus aegyptii, Hoplolaimus californicus, Hoplolaimus columbus, Hoplolaimus galeatus, Hoplolaimus indicus, Hoplolaimus magnislylus, aimus pararobustus, Longidorus africanus, Longidorus breviannulatus, Longidorus elongatus, orus laevicapitatus, Longidorus vineacola and the rasites orus Spp. in l, Meloidogyne acronea, ogyne afrz'cana, Meloidogyne arenaria, Meloidogyne arenaria thamesi, Meloidogyne artiella, Meloidogyne chilwoodi, Meloidogyne coffeicola, Meloz'dogyne ethiopica, Meloidogyne exigua, Meloidogyne graminicola, Meloidogyne gramim's, ogyne hapla, Meloidogyne incognita, Meloidogyne incognita acrita, Meloidogyne ca, Meloidogyne nsis, Meloidogyne naasi, Meloidogyne paranaensis, Meloidogyne thamesi and the sedentary parasites Meloidogyne Spp. in general, Meloinema Spp., Nacobbus aberrans, Neolylenchus vigissi, Paraphelenchus pseudoparietinus, Paratrichodorus allius, Param'chodorus lobalus, Paralrichodoms minor, Param'chodorus nanus, Paratrichodorus porosus, Param'chodorus teres and Paratrz’chodorus Spp. in general, Paralylenchus hamatus, Paralylenchus minutus, Paralylenchus projectus and lenchus Spp. in general, Pralylenchus , Pralylenchus _ 12 _ allem', Pralylenchus andinus, enchus brachyurus, Pralylenchus cerealis, Pralylenchus cofl’eae, Pralylenchus crematus, Pralylenchus rei, enchus giibbicaudatus, Pralylenchus goodeyi, Pralylenchus hamatus, Pralylenchus hexincisus, Pralylenchus loosi, Pralylenchus neglectus, Pralylenchus penetrans, Pralylenc/ms pratensis, Pralylenchus scribneri, Pralylenchus teres, Pralylenchus thomei, Pralylenchus vulnus, Pralylenchus zeae and the migratory endoparasites Pralylenchus Spp. in general, Pseudohalenchus minutus, Psilenchus magnidens, Psilenchus tumidus, Punctodera chalcoensz's, Quinisulcius acutus, Radopholus citrophilus, Radopholus Similis, the migratory endoparasites Radopholus spp. in l, Rolylenchulus borealis, Rotylenchulus parvus, nchulus rem'formis and Rotylenchulus Spp. in general, nchus laurentinus, Rolylenchus macrodoratus, Rolylenchus robustus, Rolylenchus uniformis and Rotylenchus Spp. in general, Scutellonema brachyurum, Scutellonema bradys, Scutellonema clathricaudatum and the migratory endoparasites Scutellonema Spp. in general, Subanguina radiciola, Tetylenchus nicotianae, Trichodorus cylindricus, Trichodorus minor, Trichodorus primitivus, Trichodorus proximus, Trichodorus Similis, Trichodorus Sparsus and the ectoparasites Trichodoms Spp. in l, Tylenchorhynchus agri, Tylenchorhynchus brassicae, Tylenchorhynchus clams, Tylenchorhynchus claytoni, horhynchus digitatus, Tylenchorhynchus ebriensis, Tylenchorhynchus maximus, Tylenchorhynchus nudus, Tylenchorhynchus vulgaris and Tylenchorhynchus spp. in general, Tylenchulus semipenetmns and the semiparasites Tylenchulus Spp. in general, Xiphinema americanum, ema brevicolle, Xiphinema cides comprising as an active ingredient a compound of formula (I) are suitable for the control of nematodes in soil in the fields of fruit trees, vegetables, other crops and ornamental plants.
Examples ofnematodes to which a nematicide of the t invention is applicable include, but are not limited to, nematodes of the genus Meloidogyne such as the southern root-knot nematode (Meloidogyne incognita), Javanese root-knot nematode (Meloidogyne ca), northern root-knot nematode (Meloidogyne , and peanut root-knot nematode (Meloidogyne arenaria); nematodes of the genus Ditylenchus such as the potato rot nematode (Ditylenchus destructor) and bulb and stem nematode (Ditylenchus dipsaci); nematodes of the genus Pratylenchus such as the cob root-lesion nematode (Pratylenchus penetrans), Chrysanthemum root-lesion nematode (Pratylenchus fallax), coffee esion nematode (Pratylenchus e), tea root-lesion nematode (Pratylenchus loosi), and walnut root-lesion nematode (Pratylenchus vulnus); nematodes of the genus Globodera such as the golden nematode (Globodera rostochiensis) and potato cyst nematode dera pallida); nematodes of the genus Heterodera such as the soybean cyst nematode (Heterodera glycines) and sugar beet cyst de (Heterodera schachtii); nematodes of the genus Aphelenchoides such as the rice white-tip nematode (Aphelenchoides besseyi), Chrysanthemum foliar de (Aphelenchoides ritzemabosi), and erry nematode (Aphelenchoides iae); nematodes of the genus Aphelenchus such as the mycophagous de (Aphelenchus avenae); nematodes of the genus Radopholus such as the burrowing nematode (Radopholus similis); nematodes of the genus Tylenchulus such as the citrus ‐ 13 ‐ A related aspect of the invention is the use of compounds as described herein for the preparation of itions which can be used as anthelmintic. _ 14 _ least two compounds as defined herein with a surfactant or diluent normally used in nematicidal compositions.
In particular, the present invention relates to cidal ition developed to be used in agriculture or horticulture. These nematicidal compositions may be prepared in a manner known per se.
The present invention further provides formulations, and ation forms prepared from them, as crop protection agents and/or pesticidal agents, such as drench, drip and spray liquors, comprising at least one of the active compounds of the invention. The application forms may comprise further crop protection agents and/or idal , and/or ty-enhancing adjuvants such as penetrants, examples being vegetable oils such as, for example, rapeseed oil, sunflower oil, mineral oils such as, for example, liquid paraffins, alkyl esters of vegetable fatty acids, such as rapeseed oil or soybean oil methyl esters, or alkanol alkoxylates, and/0r spreaders such as, for example, alkylsiloxanes and/or salts, es being c or inorganic ammonium or phosphonium salts, examples being ammonium sulphate or diammonium hydrogen phosphate, and/or retention promoters such as dioctyl sulphosuccinate or hydroxypropylguar polymers and/or humectants such as glycerol and/or fertilizers such as ammonium, potassium or phosphorous fertilizers, for example.
Examples of typical formulations include water-soluble s (SL), emulsifiable concentrates (EC), emulsions in water (EW), suspension concentrates (SC, SE, FS, OD), water-dispersible granules (WG), granules (GR) and capsule concentrates (CS); these and other possible types of formulation are described, for example, by Crop Life lntemational and in Pesticide Specifications, Manual on development and use of FAO and WHO cations for pesticides, FAO Plant Production and Protection Papers — 173, prepared by the FAQ/WHO Joint Meeting on Pesticide cations, 2004,1SBN: 9251048576. The formulations may comprise active agrochemical compounds other than one or more active compounds of the ion.
The formulations or application forms in on preferably comprise auxiliaries, such as extenders, solvents, spontaneity promoters, carriers, emulsifiers, dispersants, frost protectants, es, thickeners and/or other auxiliaries, such as adjuvants, for example. An adjuvant in this context is a component which enhances the biological effect of the formulation, without the component itself having a biological effect. Examples of adjuvants are agents which promote the retention, spreading, attachment to the leaf surface, or penetration.
These ations are produced in a known manner, for example by mixing the active compounds with auxiliaries such as, for example, extenders, solvents and/or solid carriers and/or further aries, such as, for example, surfactants. The ations are prepared either in suitable plants or else before or during the application. _ 15 _ Suitable for use as auxiliaries are nces which are suitable for imparting to the formulation of the active nd or the application forms prepared from these formulations (such as, e. g., usable crop protection , such as spray liquors or seed dressings) particular properties such as certain physical, technical and/or biological properties.
Suitable extenders are, for example, water, polar and nonpolar organic chemical liquids, for example from the classes of the aromatic and non-aromatic hydrocarbons (such as ns, alkylbenzenes, alkylnaphthalenes, chlorobenzenes), the alcohols and polyols (which, if appropriate, may also be substituted, etherified and/or esterified), the s (such as acetone, exanone), esters (including fats and oils) and (poly)ethers, the unsubstituted and substituted amines, amides, lactams (such as Nalkylpyrrolidones) and lactones, the sulphones and sulphoxides (such as dimethyl xide).
If the extender used is water, it is also possible to employ, for e, organic solvents as auxiliary solvents. Essentially, suitable liquid solvents are: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated ics and chlorinated aliphatic arbons 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 and also their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as ylformamide and dimethyl sulphoxide, and also water.
In ple it is le to use all suitable solvents. Suitable solvents are, for example, aromatic hydrocarbons, such as , toluene or alkylnaphthalenes, for example, chlorinated aromatic or aliphatic hydrocarbons, such as chlorobenzene, chloroethylene or methylene chloride, for e, aliphatic hydrocarbons, such as cyclohexane, for example, ns, petroleum fractions, mineral and vegetable oils, alcohols, such as methanol, ethanol, isopropanol, butanol or glycol, for example, and also their ethers and esters, s such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, for example, ly polar solvents, such as dimethyl sulphoxide, and water.
All suitable carriers may in principle be used. Suitable carriers are in particular: for example, ammonium salts and ground natural minerals such as kaolins, clays, talc, chalk, , attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and natural or tic silicates, resins, waxes and/or solid fertilizers. Mixtures of such carriers may likewise be used. Carriers suitable for granules include the following: for example, crushed and fractionated natural minerals such as calcite, marble, pumice, sepiolite, dolomite, and also synthetic granules of inorganic and organic meals, and also granules of organic material such as sawdust, paper, coconut shells, maize cobs and tobacco stalks.
Liquefied gaseous extenders or solvents may also be used. Particularly suitable are those extenders or carriers which at standard temperature and under standard pressure are gaseous, examples being aerosol _ 16 _ propellants, such as nated hydrocarbons, and also butane, propane, nitrogen and carbon dioxide.
Examples of emulsifiers and/or ormers, dispersants or wetting agents having ionic or nonionic properties, or mixtures of these surface-active substances, are salts of polyacrylic acid, salts of lignosulphonic acid, salts of phenolsulphonic acid or naphthalenesulphonic acid, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, with substituted phenols (preferably alkylphenols or arylphenols), salts of sulphosuccinic esters, taurine derivatives 5 (preferably alkyltaurates), phosphoric esters of hoxylated alcohols or phenols, fatty acid esters of polyols, and derivatives of the compounds containing tes, sulphonates and phosphates, examples being Alkylaryl ycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, protein hydrolysates, lignin—sulphite waste liquors and methylcellulose. The presence of a surface-active substance is advantageous if one of the active compounds and/or one of the inert carriers is not soluble in water and if application takes place in water.
Further auxiliaries that may be t in the formulations and in the application forms derived from them include colorants such as inorganic pigments, es being iron oxide, um oxide, Prussian Blue, and organic dyes, such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and nutrients and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
Stabilizers, such as low-temperature stabilizers, preservatives, antioxidants, light stabilizers or other agents which e chemical and/or physical stability may also be present. Additionally present may be foam-formers or ers.
Furthermore, the formulations and application forms d from them may also comprise, as additional auxiliaries, stickers such as carboxymethylcellulose, natural and synthetic polymers in powder, granule or latex form, such as gum , polyvinyl alcohol, nyl e, and also natural phospholipids, such as ins and lecithins, and synthetic phospholipids. Further possible auxiliaries include l and vegetable oils.
There may possibly be further auxiliaries present in the formulations and the application forms derived from them. Examples of such additives include fragrances, protective colloids, binders, adhesives, thickeners, thixotropic substances, penetrants, retention promoters, stabilizers, sequestrants, complexing agents, humectants and ers. Generally speaking, the active compounds may be combined with any solid or liquid additive commonly used for formulation purposes.
Suitable retention promoters include all those substances which reduce the c surface tension, such as dioctyl sulphosuccinate, or increase the viscoelasticity, such as hydroxypropylguar rs, for example.
Suitable penetrants in the present context include all those substances which are lly used in order to enhance the penetration of active agrochernical compounds into plants. Penetrants in this context are WO 64460 _ 17 _ defined in that, from the ally aqueous) application liquor and/or from the spray coating, they areable to penetrate the cuticle of the plant and thereby increase the mobility of the active compounds in thecuticle. This property can be determined using the method described in the literature (Baur et al., 1997, Pesticide Science 51, 131-152). Examples include alcohol alkoxylates such as coconut fatty ethoxylate (10) or decyl ethoxylate (12), fatty acid esters such as rapeseed or soybean oil methyl esters, fatty amine alkoxylates such as tallowamine ethoxylate (15), or ammonium and/or phosphonium salts such as ammonium sulphate or diammonium hydrogen phosphate, for example.
The formulations ably comprise between 0.00000001% and 98% by weight of active nd or, with ular preference, n 0.01% and 95% by weight of active compound, more ably between 0.5% and 90% by weight of active compound, based on the weight of the formulation.
The active compound content of the application forms (crop protection products) prepared from the formulations may vary Within wide ranges. The active compound concentration of the application forms may be situated typically n 0.00000001% and 95% by weight of active compound, preferably between 0.00001% and 1% by weight, based on the weight of the application form. Application takes place in a customary manner adapted to the application forms.
The compounds are applied in a customary manner appropriate for the use forms.
All plants and plant parts can be treated in accordance with the invention. Plants are understood here to mean all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants may be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering s or combinations of these methods, including the transgenic plants and including the plant varieties which are protectable and non-protectable by plant breeders’ rights. Parts of plants shall be understood to mean all above-ground and below-ground parts and organs of plants, such as shoot, leaf, flower and root, examples ing leaves, s, stems, , flowers, fruit bodies, fruits and seeds, and also roots, tubers and rhizomes. The plant parts also include harvested material and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, slips and seeds.
The inventive treatment of the plants and plant parts with the active ingredients is effected directly or by allowing them to act on the surroundings, habitat or storage space thereof by the customary treatment methods, for example by g, spraying, evaporating, g, scattering, painting on, injecting, and, in the case of propagation material, especially in the case of seeds, also by applying one or more coats.
As already mentioned above, it is possible to treat all plants and their parts in accordance with the invention. In a preferred embodiment, wild plant s and plant cultivars, or those obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and also parts thereof, are treated. In a further preferred embodiment, transgenic plants and plant ars ed by genetic _ 18 _ engineering, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated. The terms "parts" or "parts of plants" or "plant parts" have been explained above.
More preferably, plants of the plant cultivars which are each commercially available or in use are treated in accordance with the invention. Plant ars are understood to mean plants having new properties ("traits") and which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. They may be cultivars, biotypes and genotypes.
Depending on the plant species or plant ars, and the location and growth conditions (soils, climate, vegetation period, diet) thereof, the inventive treatment may also result in superadditive ("synergistic") effects. For example, possibilities include reduced application rates and/or broadening of the activity um and/or an increase in the activity of the compounds and compositions usable in accordance with the invention, better plant growth, increased tolerance to high or low atures, increased tolerance to drought or to levels of water or soil salinity, enhanced flowering performance, easier harvesting, accelerated ripening, higher yields, higher quality and/or higher nutritional value of the harvested products, sed e life and/or processibility of the harvested products, which exceed the effects normally to be expected.
The transgenic plants or plant cultivars (those obtained by genetic engineering) which are to be treated with preference in accordance with the invention include all plants which, through the genetic modification, received genetic material which imparts particular advantageous usefial properties ("traits") to these plants. Examples of such properties are better plant growth, increased tolerance to high or low temperatures, sed tolerance to drought or to levels of water or soil ty, enhanced flowering performance, easier harvesting, accelerated ng, higher yields, higher quality and/or a higher nutritional value of the harvested products, better e life and/or processibility of the harvested products. Further and particularly emphasized examples of such properties are an improved defence of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fiJngi, bacteria and/or viruses, and also increased tolerance of the plants to certain herbicidally active ingredients. Examples of transgenic plants include the important crop plants, such as cereals (wheat, rice), maize, soya, potatoes, sugar beet, es, peas and other ble types, cotton, tobacco, oilseed rape, and also fruit plants (with the fruits of apples, pears, citrus fruits and ), particular emphasis being given to maize, soya, potatoes, cotton, tobacco and oilseed rape. Traits that are particularly emphasized are improved e of the plants against s, arachnids, nematodes, slugs and snails by toxins formed in the plants, especially those formed in the plants by the genetic material from Bacillus thuringiensis (for example by the genes a), CryIA(b), c), CryHA, CryIIIA, CryHIBZ, Cry9c, Cry2Ab, Cry3Bb and CryIF, and also ations thereof) (referred to hereinafter as "Bt "). Traits that are also particularly emphasized are the ed defence of plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and _ 19 _ also resistance genes and correspondingly expressed proteins and toxins. Traits that are additionally ularly emphasized are the increased tolerance of the plants to n active herbicidal ingredients, for example imidazolinones, sulphonylureas, glyphosate or phosphinothricin (for example the "PAT" gene). The genes which impart the d traits in on may also be present in combinations with one another in the transgenic plants. Examples of "Bt plants" include maize ies, cotton varieties, soya varieties and potato varieties which are sold under the trade names YIELD GARD® (for example maize, cotton, soya), KnockOut® (for example maize), StarLink® (for example maize), Bollgard® n), Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide—tolerant plants include maize varieties, cotton varieties and soya varieties which are sold under the trade names Roundup Ready® (tolerance to glyphosate, for example maize, cotton, soya), y Link® (tolerance to phosphinothricin, for example oilseed rape), IMI® (tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, for example maize). Herbicide-resistant plants (plants bred in a conventional manner for ide tolerance) which may be mentioned include the varieties sold under the name ield® (for example maize). Of course, these statements also apply to plant cultivars which have these genetic traits or genetic traits which are still to be developed and will be developed and/or marketed in the future.
The plants listed can be treated in accordance with the invention in a ularly advantageous manner with the compounds of the general formula (1) and/or the active ingredient mixtures according to the invention. The preferred ranges stated above for the active ingredients or mixtures also apply to the treatment of these plants. Particular emphasis is given to the treatment of plants with the compounds or mixtures specifically mentioned in the present text.
The inventive active ingredient may be present in its commercially available ations and in the use forms, prepared from these formulations, as a mixture with other active ingredients, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators, ides, safeners, fertilizers 0r semiochemicals. The mixtures thus obtained have a broadened spectrum of activity.
Mixtures with flingicides are particularly advantageous. Examples of le fungicide mixing partners can be selected from the list consisting of (l) Inhibitors of the ergosterol biosynthesis, for example aldimorph, azaconazole, bitertanol, onazole, onazole, diclobutrazole, difenoconazole, diniconazole, diniconazole-M, rph, rph acetate, epoxiconazole, azole, fenarimol, fenbuconazole, fenhexamid, fenpropidin, fenpropimorph, fluquinconazole, flurprimidol, flusilazole, flutriafol, furconazole, furconazole-cis, hexaconazole, imazalil, imazalil sulfate, imibenconazole, ipconazole, metconazole, myclobutanil, naftifine, nuarimol, nazole, paclobutrazol, pefurazoate, penconazole, piperalin, prochloraz, propiconazole, prothioconazole, pyributicarb, pyrifenox, quinconazole, simeconazole, spiroxamine, tebuconazole, terbinafme, onazole, triadimefon, triadimenol, tridemorph, triflumizole, _ 20 _ triforine, triticonazole, uniconazole, uniconazole-p, Viniconazole, voriconazole, l-(4- chlorophenyl) (1H- 1 riazol- l -yl)cycloheptanol, methyl -dimethyl-2, 3 -dihydro-lH-inden-l -yl)-1H- imidazole-S-carboxylate, N'— {5-(difluoromethyl)methyl [3 -(trimethylsilyl)propoxy]phenyl} -N- ethyl-N—methylimidoformamide, N—ethyl-N—methyl-N'- {2-methyl-5 -(trifluoromethyl) [3 - (trimethylsilyl)propoxy]phenyl}imidoformamide and O-[l-(4-methoxyphenoxy)- 3,3-dimethylbutan—2- yl] lH-imidazole- l -carbothioate. (2) inhibitors of the respiratory chain at complex I or II, for example bixafen, boscalid, carboxin, diflumetorim, fenfiiram, fluopyram, flutolanil, fluxapyroxad, furametpyr, furmecyclox, isopyrazam re of syn-epimeric racemate lRS,4SR,9RS and anti-epimeric racemate lRS,4SR,9SR), isopyrazam (anti-epimeric racemate lRS,4SR,9SR), isopyrazam (anti-epimeric omer 1R,4S,9S), isopyrazam (anti-epimeric enantiomer lS,4R,9R), isopyrazam (syn epimeric racemate lRS,4SR,9RS), isopyrazam (syn-epimeric enantiomer lR,4S,9R), azam (syn-epimeric enantiomer lS,4R,9S), mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, thifluzamide, l-methyl-N—[2-(l,l,2,2- uoroethoxy)phenyl] -3 -(trifluoromethyl)-1H-pyrazolecarboxamide, 3 -(difluoromethyl)-l - methyl-N— [2-(1 ,1 ,2,2-tetrafluoroethoxy)phenyl] - l H-pyrazolecarboxamide, 3 -(difluoromethyl)-N- [4- fluoro-Z-(l , 1 ,2,3 ,3,3 -hexafluoropropoxy)phenyl] -l -methyl-1H-pyrazolecarboxamide, N—[l -(2,4- dichlorophenyl)- l -methoxypropan—2-yl] -3 -(difluoromethyl)- l -methyl-1H-pyrazolecarboxamide, 5,8- difluoro-N— fluoro-4 - {[4-(trifluoromethyl)pyridin—2-yl] oxy} phenyl)ethyl]quinazolin—4-amine, N- [9-(dichloromethylene)- l ,2, 3 ,4-tetrahydro- l ,4-methanonaphthalen—5 -yl] (difluoromethyl)methyl- azolecarboxamide, N— [(l S,4R)(dichloromethylene)- l ,2,3,4-tetrahydro- l ,4- methanonaphthalen—5-yl]-3 -(difluoromethyl)methyl- 1 H-pyrazolecarboxamide and N— [( l R,4 S) (dichloromethylene)— l ,2, 3 ,4—tetrahydro— 1 ,4—methanonaphthalen—5—yl] —3 —(difluoromethyl)— 1 —methyl— alyrazole—4—carboxamide. (3) inhibitors of the respiratory chain at complex III, for example ametoctradin, amisulbrom, azoxystrobin, cyazofamid, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, famoxadone, fenamidone, fenoxystrobin, fluoxastrobin, kresoxim—methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, ystrobin, pyribencarb, triclopyricarb, ystrobin, (2E)-2—(2- {[6-(3-chloromethylphenoxy)fluoropyrimidin—4 - yl] enyl)(methoxyimino)-N—methylethanamide, (2E)(methoxyimino)-N-methyl(2- {[( {(lE)- l - [3 -(trifluoromethyl)phenyl] dene} amino)oxy]methyl} phenyl)ethanamide, (2E) xyimino)-N-methyl-2— {2- [(E)-( { l - [3-(trifluoromethyl)phenyl] ethoxy} imino)methyl]phenyl} - ethanamide, (2E) {2-[({[(1E)(3 - {[(E)- l -fluoro-2—phenylethenyl] oxy} )ethylidene] amino} - oxy)methyl]phenyl} (methoxyimino)-N-methylethanamide, (2E)-2— {2- [( { [(2E,3E)(2,6- dichlorophenyl)but-3 -en—2-ylidene] amino} oxy)methyl]phenyl} (methoxyimino)-N—methylethanamide, 2-chloro-N—(1 ,l ,3 -trimethyl-2,3-dihydro-1H-indenyl)pyridinecarboxamide, 5-methoxy—2-methyl- 4-(2- {[( {(1E)- l -[3 -(trifluoromethyl)phenyl]ethylidene} amino)oxy]methyl} phenyl)-2,4-dihydro-3H- _ 21 _ 1,2,4-triazolone, methyl (2E)-2— {2-[( {cyclopropyl[(4-methoxyphenyl)imino]methyl} - sulfanyl)methyl]phenyl} -3 -methoxyprop-2—enoate, N—(3 - ethyl-3 ,5, 5 -trimethylcyclohexyl)-3 - (formyl- amino)hydroxybenzamide, 2- ,5-dimethylphenoxy)methyl]phenyl} methoxy-N—methylacet- amide and 5 (2R)—2- {2-[(2,5-dimethylphenoxy)methyl]phenyl}methoxy—N—methylacetamide. (4) Inhibitors of the mitosis and cell division, for example l, carbendazim, enazole, diethofencarb, ethaboxam, fluopicolide, fuberidazole, uron, thiabendazole, thiophanate-methyl, thiophanate, de, 5-chloro(4-methylpiperidin-l-yl)(2,4,6-trifluorophenyl)[l ,2,4]triazolo[1,5- a] pyrimidine and 3 -chloro(6-chloropyridin-3 -yl)—6-methyl(2,4,6-trifluorophenyl)pyridazine. (5) Compounds capable to have a multisite action, for example bordeaux mixture, captafol, captan, chlorothalonil, copper hydroxide, copper naphthenate, copper oxide, copper oxychloride, copper(2+) sulfate, dichlofluanid, dithianon, dodine, dodine free base, ferbam, fluorofolpet, folpet, guazatine, guazatine acetate, tadine, iminoctadine albesilate, iminoctadine triacetate, mancopper, mancozeb, maneb, metiram, metiram zinc, oxine-copper, propamidine, propineb, sulphur and sulphur preparations including calcium lphide, thiram, tolylfluanid, zineb and ziram. (6) Compounds capable to induce a host defence, for example acibenzolar-S-methyl, isotianil, probenazole and tiadinil. (7) Inhibitors of the amino acid and/or protein biosynthesis, for example andoprim, blasticidin—S, cyprodinil, kasugamycin, kasugamycin hydrochloride hydrate, mepanipyrim, pyrimethanil and 3-(5- fluoro-3 ,3,4,4-tetramethyl-3 ,4-dihydroisoquinolin— l -yl)quinoline. (8) tors of the ATP production, for example fentin acetate, fentin chloride, fentin hydroxide thiofam. (9) Inhibitors of the cell wall sis, for example benthiavalicarb, dimethomorph, flumorph, iprovalicarb, mandipropamid, polyoxins, polyoxorim, mycin A and valifenalate. (10) Inhibitors of the lipid and membrane synthesis, for example biphenyl, chloroneb, dicloran, edifenphos, etridiazole, iodocarb, iprobenfos, isoprothiolane, propamocarb, ocarb hydrochloride, prothiocarb, phos, quintozene, tecnazene and tolclofos-methyl. (l l) Inhibitors of the melanine biosynthesis, for example carpropamid, diclocymet, fenoxanil, phthalide, pyroquilon, lazole and 2,2,2-trifluoroethyl {3-methyl-l ethylbenzoyl)amino]butan—2- yl} carbamate. (12) Inhibitors of the nucleic acid synthesis, for example benalaxyl, benalaxyl-M (kiralaxyl), bupirimate, clozylacon, dimethirimol, ethirimol, furalaxyl, hymexazol, metalaxyl, metalaxyl-M oxam), ofurace, oxadixyl and oxolinic acid. 2012/071385 _ 22 _ (13) Inhibitors of the signal transduction, for example chlozolinate, fenpiclonil, fludioxonil, iprodione, idone, quinoxyfen 5 and Vinclozolin. (14) Compounds capable to act as an uncoupler, for example binapacryl, dinocap, ferimzone, fluazinam and meptyldinocap. (15) Further compounds, for example benthiazole, bethoxazin, capsimycin, carvone, chinomethionat, enone (chlazafenone), cufraneb, cyflufenamid, cymoxanil, cyprosulfamide, dazomet, debacarb, dichlorophen, diclomezine, difenzoquat, difenzoquat sulphate, diphenylamine, ecomate, fenpyrazamine, flumetover, fluoroimide, flusulfamide, flutianil, l—aluminium, fosetyl—calcium, fosetyl—sodium, hexachlorobenzene, irumamycin, ulfocarb, methyl isothiocyanate, metrafenone, mildiomycin, natamycin, nickel dimethyldithiocarbamate, nitrothal-isopropyl, octhilinone, oxamocarb, oxyfenthiin, pentachlorophenol and salts, phenothrin, phosphorous acid and its salts, propamocarb- fosetylate, propanosine-sodium, proquinazid, pyrimorph, (2E)—3-(4-tert-butylphenyl)-3 -(2- pyridinyl)(morpholinyl)propen-1 -one, (ZZ)-3 -(4-tert-butylphenyl)-3 -(2-chloropyridin— 4-yl)(morpholinyl)propenone, pyrrolnitrine, tebufloquin, teclofialam, tolnifanide, triazoxide,trichlamide, zarilamid, (3 S,6S,7R,8R)benzyl[({3-[(isobutyryloxy)methoxy] methoxypyridin—Z-yl } carbonyl)amino] methyl-4,9-dioxo- 1 ,5-dioxonan—7 -yl 2-methylpropanoate, 1-(4- {4-[(5R)—5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3 ,3 olyl}piperidin—l -yl) [5- methyl-3 -(trifluoromethyl)- 1 zolyl]ethanone, 1-(4- {4- [(5S)(2,6-difluorophenyl)-4,5- dihydro-1,2-oxazol-3 -yl]-1,3 -thiazolyl}piperidin—1-yl)[5-methyl-3 -(trifluoromethyl)- 1 H-pyrazol- 1-yl]ethanone,1-(4-{4-[5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazolyl]-1,3-thiazolyl}piperidin— 1-yl)-2 - [5-methyl-3 -(trifluoromethyl)-1H-pyrazol-1 -yl] ne, ethoxyphenoxy)-3 ,3 -dimethylbutan —Z-yl- 1 H-imidazole- 1 xylate, 2,3,5,6-tetrachloro(methylsulfonyl)pyridine, 2,3 - dibutylchlorothieno[2,3 imidin—4(3H)-one, 2,6-dimethyl-1H,5H-[l ,4]dithiino[2,3-c:5,6- c']dipy1role- 1 ,3,5,7(2H,6H)-tetrone, 2-[5-methyl(trifluoromethyl)- l H-pyrazolyl]—1-(4- {4-[(5R) phenyl-4,5-dihydro-l,2—oxazolyl]-l,3-thiazolyl}piperidin—1-yl)ethanone, 2- [5-methyl-3 - (trifluoromethyl)-alyrazol-l-yl]—l-(4-{4-[(5S)phenyl-4,5-dihydro-1,2-oxazolyl]-1,3-thiazol—2- yl}piperidin—l-yl)ethanone, 2-[5-methyl—3-(trifluoromethyl)-lH-pyrazol-l-yl]{4-[4-(5-phenyl-4,5- dihydro- 1 ,2-oxazol-3 -yl)- l ,3 -thiazol-2—yl]piperidin—1 -yl} ethanone, 2—butoxyiodopropyl-4H- chromen—4-one, 2—chloro[2—chloro(2,6-difluoromethoxyphenyl)methyl-lH-imidazol-S- yl]pyridine, 2-phenylphenol and salts, 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-lyl )quinoline, trichloropyridine-Z,6-dicarbonitrile, 3-[5-(4-chlorophenyl)-2,3-dimethyl-l,2- oxazolidinyl]pyridine, 3-chloro(4-chlorophenyl)—4-(2,6-difluorophenyl)methylpyridazine, 4-(4- chlorophenyl)(2,6-difluorophenyl)-3,6-dimethylpyridazine, 5-amino- 1 ,3 ,4-thiadiazolethiol, 5- chloro-N'-phenyl-N'-(propyn— 1 -yl)thiophenesulfonohydrazide, 5-fluoro [(4-fluorobenzyl) - oxy]pyrimidin—4-amine, 5-fluoro[(4-methylbenzyl)oxy]pyrimidin—4-amine, 5-methyloctyl- [1,2,4]triazolo[l,5-a]pyrimidinamine, ethyl (ZZ)aminocyanophenylpropenoate, N'—(4-{[3- _ 23 _ (4-chlorobenzyl)- 1 ,2,4-thiadiazol-5 -yl] oxy} -2, 5 -dimethylphenyl)-N-ethyl-N—methylimidoformamide, N- orobenzyl)-3 - [3-methoxy(propyn— 1 -yloxy)phenyl]propanamide, N- [(4- chlorophenyl)(cyano)methyl]-3 - [3 -methoxy—4-(propyn— 1 -yloxy)phenyl]propanamide, N— [(5-bromo-3 - chloropyridinyl)methyl] -2,4-dichloropyridine-3 -carboxamide, N—[l -(5-bromo-3 -chloropyridin—2- yl)ethyl] -2,4- dichloropyridine-3 -carboxamide, N— [l -(5-bromo-3 opyridin—2-yl)ethyl] fluoro iodopyridine-3 -carboxamide, N- {(E)-[(cyclopropylmethoxy)imino] [6-(difluoromethoxy) -2,3 - difluorophenyl]methyl} nylacetamide, N— {(Z)— [(cyclopropylmethoxy)imino] [6—(difluoromethoxy) — 2, 3 —difluorophenyl]methyl} —2—phenylacetamide, N'— {4— [(3 butyl—4—cyano—1,2—thiazol—5—yl)oxy]—2 — chloro—5 —methylphenyl} —N—ethyl—N—methylimidoformamide, N—methyl—2— (1 — { [5—methyl—3 — (trifluoromethyl)- 1 H-pyrazolyl] acetyl} dinyl)-N-(1 ,2, 3 ,4-tetrahydronaphthalenyl)- 1 ,3 - thiazolecarboxamide, N-methyl(1 - { [5-methyl(trifluoromethyl)- 1 H-pyrazolyl] acetyl} - piperidinyl)-N—[(1R)-1,2, 3,4-tetrahydronaphthalen-1 -yl]-1, 3 -thiazolecarboxamide, N—methyl(l - {[5-methyl(trifluoromethyl)- 1 H-pyrazolyl] acetyl }pip yl)-N—[(1S)-1,2, 3 ,4-tetrahydro- naphthalen—l -yl]-1, 3 -thiazolecarboxamide, pentyl {6-[( { [(1-methyl-1H-tetrazol-5 henyl) - methylidene] amino} oxy)methyl]pyridin—2 -yl} carbamate, phenazinecarboxylic acid, in—8 - ol, quinolin— 8 - ol sulfate (2: 1) and tert-butyl {6- [( { [(1 -methyl-1H-tetrazol-5 -yl) (phenyl) - methylene] amino} oxy)methyl]pyridin—2-yl} carbamate.
The active ingredients specified herein by their "common name" are known and described, for example, in the Pesticide Manual ("The Pesticide Manual", 14th Ed., British Crop Protection Council 2006) or can be ed in the intemet (e. g. http://Www.alanwood.net/pesticides).
The composition according to the invention comprising a mixture with a bactericide compound may also be ularly advantageous. Examples of suitable icide mixing partners may be selected in the list consisting of bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, fiJrancarboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.
The various aspects of the invention will now be illustrated with nce to the following tables of compounds and examples. The following tables illustrate in a non limiting manner examples of compounds according to the invention.
Abbreviations which are used in the tables e the following: M6 2 CH3 E1 = (:sz l’l-PI‘ = CH2CH2CH3 _ 24 _ tert butyl = C(CH3)3 = t-Bu Pr = cyclopropyl C6H5 = phenyl comm. W. = commercially available 2012/071385 .E0 EE £2:qu 856803 E E mzz SE 52:qu 253005 N E22 N E E E E ESE E .an E E E22 E N038 E 33an E EQN EQN m mEoN m m am 5 5 5 EN E6 20 6N 6-0 m 6+ 8: - - - N N N I mm E m E m m m m m E m m H E E E E E E E E E E E mm I mEEO EEO m m m m Emmzoo Emmzoo Emmzoo Emmzoo mm 22000 m E £000 m £08 m m E m m 0 0 R 22000 m E £000 2000 2000 :0 m E m m 2353 N 6 6Eu H - mmO-m we in I m Wm Eva 6% m -m 6% flow 66 ENE m 6% Eva Eva £3 Eva flow 6% «ENE mcnsomEoU E 52 ENE N-NE m m o n w a S -w 1E a. .N km IN -5 E E E E E E .6 E ENE WO 64460 8m Sm mom Sm mm Em 2m Sm :m as 8m Em Rm Em am 0% .20 . . . . . . . . . . . . .3 E 90 UE90 E UE90 E .ch UE90 UEmo cE90 UE90 E .ch uEno UE90 UE90 UE90 E .30 cE90 E Noz-m m Eo-m m an a o E-N 6.0 m m - S-N @204" find-w S-N Eo-o Waco-v E-N U-N G-o E-N v 020-? Eo-m 020-? E m m m m m m m m m m m m m m m m m H m E m m E m E E m m m m m m m m m mm E560 5:28 E560 Emmzoo 3:28 DEE/E8 02:28 03:28 2208 208 2208 0208 fiooo fiooo E08 E08 2208 "m m m m m m m m m m m m m m m m m m B E m m m m m m m m m m m m m m m m Eo-m m m m m m m m m m m m m an W mmI WMI S-m mEo-m WMI S-m Eo-m WMI WM- WMI Wm- S-m Eo-m WM- WMI mw-mmI mwmmI S-m MED-m WMI B-m .2 2.2 2.2 E S E 8 a 2.3 -5 IN In E 2-2 2.2 2.2 8-2 2.2 8.3 $2 3-2 E E 3-2 wN-a 2012/071385 wNm NNm 0mm Emm mmm Nmm mmm 0mm 2m wmm am CNN mm m0 .3 .25 E .30 E .30 E N3 E .30 E E E N N E E E EEO E .30 E .30 E .25 E E E .30 E .30 E N3 NE E22 E .30 E .690 E N m N N N N N m an 6 m E N. 5 6 m - 02 5 E - oz o - 02 5 - SN SN 5 5 N - - N - N - - N - I m m m m m NEoN NEQN N N NEoN mm E E E E E E E E E E E E E E E E E Nm EE E EE E E E E E E E E E E E EE E E o 0 0 0 0 0 0 Nm 2000 208 2000 Emooo Emooo Emooo Emooo SEE/E8 SEE/E8 SEE/Eco SEE/E8 EEooo 0 m m 2 m m NM m E E E E E E E E E E E E E E EEO NEEQNEEU ENE m E E E E E E E E E E m mEEo mEEO E E3 Eva ENE Eva Eva ENE Eva Eva ENE Eva ENE Eva Eva m m m Q 6N 6N EN 6N 6N SN 6N 6a 6a 6N 6N 6N Wm 5R» 5 I m I 6N Eva I 6N m m .2 NN om E Nm mm Nm mm 3 a mm om ON N NN -N. -N -N In -N -N - -s -N. -N -N In -N I E E E E E E NE E E E E E NE NN-NE E NE mNNE 3 8 3 we No S E E E N» N H N m H" Hugo .30 . .20 . . . . . . . .
.Hu N N N H HVNHmo 2H HVN,Hmo HVN,Hmo HanHmo HVNAH90 HUN,H90 HHNH90 2H 222 8 222 2H .30 ,H .80 ,H .80 HVNAHno HVNAH90 m m :2 5 H-N 20 mwHo-N H-N Hm-N mwHo-N H-N Hm-N m6- UN HH-HV Ho-N H-m Ho-N Ho-m SN 6-H" WmI - - N N N ozo-N mm H2 2 H2 H2 2 H2 H2 H2 H2 H2 2 H2 HH 2 H2 2 .wH H2 2 H2 H2 H2 H2 H2 H2 H2 H2 2 H2 HH H2 H2 2 "2 2 m 2 2 2 2 2 2 2 2 m 2 2 2 2 m N2 H2 m H2 m H2 m H2 H2 23.08 EB 2 H2 HH 2 H2 m H5 H m m m m m wH H20 28 220 Hofiwu-N-oomz N-oomz mHHo 220 Hofiwo-N-oomz 23.08 20 20 HHo mo 220 28 m flo-m www-om mHmW-w mHnHW-w m m m m m an Ho-m Ho 6 Hwy-mm mwmm Wm H m-m WM 6 6 - - - - - - - m I I I m m Ho-m Ho-m mnHo-m woo-mmI WmI m mmo-m .2 S NH- cm S mm mm 2 3-2 -6 a -5 a -5 H 3-2 092 Hm-2 NW2 NW2 Hum-2 3.2 H H H H 8-2 62 WO 64460 m 0 h w a 2 2 2 2 E 2 2 M: & ON E .3 6%6% 6M" .6va Wm .6va am .UMM 6% 6% 6% .6va mflm .6va 6% .6va 6% an Mflwflm MHWHW 32 WWW WWW WWW WM "Wm OWN MN WWW WM WNW Wm ozmz-m 22ml MHWHM E m m m m m m m m m m m m m m m m m H m m m m m m m m m m m m m m m m m mm m m m m m m m m m m m m m m m m m mm m m m m m m m m m m m m m m m m m "m Eu £0 £0 £0 £0 £0 £0 £0 Eu £0 £0 £6 £6 £8 £6 £6 £6 an WWW WWW WWW WWW WWW WWW WWW WWW WWW WWW WWW WWW WWW WWW anw Woow WWW 52 Sé 3-2 $2 8-2 8-2 no-2 W92 3-2 0:2 RE NE: m; EE m; 3-2 RE M32 WO 64460 mm 8 E mm cm R mm om om Mm mm mm 3 mm ..s 6% mzz Wm .6va am .UMM 6% 6% 6% 6% Wm .6va 6% .6va 6% am Mflwflw HE 0%va mm 2>& WWW WWW WM WWW "WWW MN WWW/WM WWW Fri £0-N Q: an: mm m E m . m m m m m m m m m m m m m H m m m . m m m m m m m m m m m m m mm m m m . m m m m m m m m m m m m m mm m m m . m m m m m m m m m m £0 £6 5-: B £6 £6 £6 £6 £6 £6 £6 £6 £6 £6 £6 £6 £0 £0 £0 E.: an WWW Wwow anw ".00.... WWW WWW WWW WWW WWW WWW WWW WWW WWW W%..% WWW Woow WWW .2 3-3 3-2 $2 3-2 5-2 £2 of: 532 wwé of: 8-3 3-2 8-2 32 $2 QE WO 64460 om R a N mm ow 3 ma 3 3 3 m a m S E 6%am am6% am 6% 6% am" 6% am 6% 6% A" 6% 6% ESWM EEWEE an E E& £3 ERN £2 E& EEo-N E: m: EEQE FERN EEQE E E ERN ERN ERN R E E E E E E E E E E E E E E E E E «E E E E E E E E E E E E E E E E E E ME E E E E E E E E E E6 220 ozARoo AER AER AER AER AER NE Ea Ea E E E E E E E0 E E E E Ea Ea E E E6 E6 E6 Ea Ea Ea E0 E E E E E E E mwnww "WM "WM "WM mwnww "WM WWW WWW WWW "WM "WM www.mm mwnww "WM WWW "Now mwnww .2 8-2 3.2 ame "3-2 872 SEE STE STE SEE 82E 872 STE HwSE "02.2 2 2 TE 5.2 TE 2012/071385 8 6 ow om E mm mm Um mm S mm 3 8 mm mm U h .3 6mm6% 6% Um .me 6mm 6% UMM 6% .me 6% 6% .me .me 6% .UMM UM" an SQN E Q: Um E 52 SEQN EQN EQN mam EPN E £3 SQN E EQN Wm R m m m m m m m E m m m m m m m E E R m m E m m m m E m m m m m m m E E mm m m £6 £6 m m m E m £0 £0 m m £0 £0 ANEOV ANEUV mm m m E E m m m 22000 m E E m m m E B Eu £0 m m mammooémdomz mammogqmdomz mammooémdomz Z0 20 m m £0 £0 £0 £0 E E an Wm WM WWW WWW WWW anw WWW "WWW WWW WWW WWW 66 6% W%.% WWW "WWW «WWW 2 3 2 2 2 2 mam mmN .2 T2 Ta TE 73 2T2 T2 72 omTwE GTE E E -3 -2 v2-3 872 02-3 RTE wNTfl 373 S 8 we 3 .Ho MSW HHSWHH N .30 N .30 MHHM/HH N.H 68 N N .H ,H ,H 690 E H30 HHSNM N .H mS/ ,H "9/ NH $7 £H\// £H\/Nw NAH £22 £o-N m m m m an £o-N 5 5 £o-N EN HN- £0 E £o-N HN - - - - HN N N N £o-N £o-N 6N 6N H H ,H H mm -o -o m H£ m m H£ H H H£ m H£ m m H£ m H£ m m 98 98 H H£ H£ H£ H£ H£ HH H£ H£ H£ H£ H£ H£ H£ HH H£ HH H£ m m m m m m mm m m H5 £0 m :0 H5 m m H5 :0 m mHHo £0 mHHo £0 mm m H£ m E m m m "H m m m HH E m H£ wH £6 £6 m m m H£ E H£ N "H m m m 0 £-oHo>o-NHHo fo NHHouwHoNHHo £-oH%o-NH£o £o-m £o-m mm0-m mmO-m £o-m £06 £o-m m m m Q 6% 6% 6-0 6N 6% 6N 6% 5N 66 6a Wm 6N 6N 6N 6a Wm HnHoo I mI WmI 6N mmvfi .2 omEH HmHaH NmH mmH o: mmH 8H RH me H: N: -N 5.2 a -w -m -N IN a a -5 H H H H H H NmHaH H H H 33H 33H H32H HSZH 2012/071385 .H0 E N30 Nz fizz E fizz NNz fizz 9H v.30 E 2% Na fizz Na fizz NNz fizz Nz fizz fizz Nz Na NNz E fizz E fizz E N N N N m "Ho H a 220 an - - - I "Ho m - - - HN HN HN HN mN NED mN NHwHo 28¢ NVHQN I NzoN N N N - - N N N 020% mm m Hz m m Hz m m HH m Hz z m onoo m m m m E 3 Hz HH m Hz Hz m HH m Hz z m Hz HH m Hz Hz N N m N H m m H5 HHo :0 Hzo z m z z N N N N NN NN H5 HHo H5 H5 £8 3H8 NzNwHoV NyH NH NH m m m m m m Hz m m I B m NH m wH Hz m m HH 0 mob 6 m m m IN -N NHzNo mo 5 @2850 02660 Nzofi m m m an 6% 5% 6a 6a 6% 6% NR3 6N 6% 6N 6% Hoa NNHo-m SN flow 6% NR3 6a Nmofi wnwmm HNHoo.
I mmI SN mHHOIm WmI 6% NR3 6N NEE 6N .2 NE m: 9: 8H HmH NNmH mmH E NEH N02 NmH NEH NNS -N In -N -N .5 -N I -N -N IN. -N -N -N H H H H H H 5-3 meNH NH 8T2 H H H H H H NmoHNH WO 64460 .8viz E mzz fizz E E22 Nm Na Nm g2 Nm $2 Na VHS/H N g7 N m Na mS/ m $7 Nm 37 Na $7 Nm $7 Nm ME? Nm #3 N m5N m 5 Hm N m - oz 5 I I EN mN a mN 3 VS mN "N MN- N- I I 6N 6-0 5-0 moN 6N 6-? m N N v - R m m m m m m m m m m m m m m m m R m m m m m m m : m m m m m m : m mm m m :08 £0 £0 :0 £0 £0 £0 £0 m £6 £6 AER REE AER mm m m m E E m E E E E m E E B m m m 508 "mo m m m m m m m m £0 £0 Eu ENE m m m m m m m m m m m m m m an 66 6 m - WWI Wm- WMI Wm I - - 5N 5% m Wm- Wm- m Wm Wm ENE Wm- Wm- Wm- Wm- WMI .2 ESE $8-3 $3-3 573 News $72 Eva E H Nzé KT: v2-3 $72 02-3 5-2 $72 3va WO 64460 .Is E E E E 8 E 8 E S E E 8 E E S S E MEZ m m m N an E Q: H - I 5 I "6 no N I E E E E E I E - I N SQN mam Q: Q: N N ozm R m m m m m m m m m m m m m m m m m R m m n m m m m m m m m : m m m m m m m m m m mo m mm m N -N u £6 mu :0 £0 £0 £0 £0 £0 £0 £00-96 £6 moEo IN o :0 mo :0 mm m E m m E E E E E E m m E m m m m m. w B mu £0 m m m m m m m m w m m o 0 £0 £0 £0 mmo £0 £0 Q 6a 5% Wm 6- "E E m #OIm 6a #UIW mi 5a Eva £3 6% #UIW Wm 6-m 5% 6a HUIW WmI 6% £3 5m mmOIm .2 9: 32-2 NM: m: ca 02 m2 m2 - I I I I - a 2 a 32.2 £73 32.2 $72 $2-3 aim Nova 3 5-2 2 v2-3 3 IN WO 64460 .H0 NH HH>/ NH HH>/ NH HS/ NH HH>/ NH HH>/ NH HH>/ NH HH>/ NH HH>/ NH HH>/ NH HS/ NH HS/ NH HS/ NH HH>/ NH HH>/ NH am 6 6 - H-N Hé H 6w- 6N 6-? 6N Ho¢ m 6N 6+ HUN Ho?. . - m - H-N Hé 6N Ho¢ 6N m HoN mm H H H H H H H H H H m m H H H E H H H H H H H H H H H H H H H R m m m m m m m m m m m m m m m NH H H H H H H m m m m m m m m H N N :672 :572 :572 :572 :57m :57 o o o o o o o O m \ \ \ \ \ \ \ \ / / / / / / / / 2 2 2 2 2 2 2 2 AmHHuVH/H Q Ho-m MRI 6a Eva 6a flea EN MRI 6a Eva 6a mHo-m 6a MRI 6a Eva 6a flea EN Eva 5a MHHE 6a flea EN Eva 6a Eva 6a .2 3H WHH 8H EN HON NON SN :N SN EN SN wON EN SN -N .5 -m -N -a -N .6 .6 .5 .6 .6 a IN km H H H H H H H H H H H H H H HNHNH 595-35 mzzmo @353 E ea a 2 £3, woafiamom BEBE BEBE :58 .3 $7 am mSmw gm MSNM SE g EOE 8w E ? 0.58 mm w 8 "flaw an £3 SHE N075 m N072 0% am: Genoa £05022st 35m x E>< $2826 as, of 8 33m Smack? "En .Aqbwmsfifiv mo a mo 682031 mm R E m m m m m m 89me £3, M89 m. s 532:5 v 08 98: .OmEDAwB box/o R m m m m m m m u "EEEBBHV :8 Boa a«GOO :08 Hm $9355 >5: 5629538 "Em: 8a 6985 "ZOMQU Eam ...A9§msfifiv 335% mm m m m £6 m m £3, nonspswmaoo 5 BEBE SE £528 $2823 MBQQEZiH mm womwoomw 8w 83:3 05 mo was $658 88% ASEEEC E mm E m m E m fiooo "meow 238nm 023% 3:2 8.8 ofimwflo 62%: 6 E 68385 fiEoEEE m Eam _ .88 8:0me E mm 935 33: 33>on 3%: afifiéé 08 mm DE $9653 5E DE B "$on £0 £0 Eu 85m 28808 m 8:5:ng 52 0:253:88an 33830 $3855 358 E 33m E Estoomwizz "HoEofiégbm 2: :3me 29888 83» as, @2023 @2023 as 53>, we an Sea "WM Wm WM "WM "mm WM Wm ofimo .33. yo E s :23 (Ho Hm: 32 use: .2 3.2 2-2 ENE :Né Smé "$88;on #27:? "www-mzz? >23sz €538 Boa— «www-mz Sgizz x89 Boa Z é£%a-m§z .2 2: BEL BEL The 1H-NMR data is ted in Fig. 1.
Page ionally left blank Page ionally left blank Page ionally left blank Page ionally left blank Page ionally left blank Page ionally left blank Page ionally left blank Page ionally left blank Page ionally left blank Page ionally left blank Page ionally left blank Page ionally left blank Page ionally left blank Page ionally left blank Page ionally left blank Page ionally left blank Page ionally left blank Page ionally left blank Page ionally left blank Page ionally left blank Page ionally left blank Page ionally left blank Page ionally left blank 2012/071385 .3 E E E E E E E E E E m 2204" 6-? EQM 5N 6-0 £00-? £2 m 220-? 5m 6-0 £64" R m m m m m m E m m m m E m m m m m m m m m m m @600 @600 £68 @600 D R $000 @600 @600 £560 $560 B200 @200 "m m m : m w m m m w m m R m m m m m m m m m m m 2358 0 0 D D 36.0 D m 0 o mo WomoI WW0I WowI WWI 5m WowI WowI Wow| WomoI 6% 36.0 6% 2&de 5:59:80 52 I: NA: we *1: m e 3: E: we 9e I a :.£ Em 8% I H .6 E mzz FL mzz E mzz E hm mzz E MHH>H7H E E mzz E hm E? E E? E mS/ KL $7 E mS/ E MHS/ E E 9:26 9+3; N O N % 0 m m am 6 6 M— - OZ 6 I 02 "HO I m m - - 5% H>HO v w I N94% - 6% 6% :6 :6 - I 6+ m I N m w m m £3 E" w mm m HIH m m HIH m m m m HIH m m HIH m m m E E m HIH m E HIH E m m m HIH m m HIH m m m m D o o o o u D R Hu..I.HHIH7HOU 2:766 0:706 6:766 6566 6:766 OU 3606 :78 H\/HIH/OU :78 3706 H\/HIH/OU 6006 6006 6006 6006 N: : HIH m : HIH : m m m HIH m m HIH m m m m B m HIH m m HIH m m m m HIH m m HIH m m m m 030% 050% 030% 90% 0 030% uSOID 25% 030% o 0 an 6% HUIW 6% WW0 HUIW 6% 6 Sm I 6% 6% % - HUIW 030% 6% 90% 6% HUIW 6% 6% o 36% 030% 050% 6% 030-0 WWWI .oz S mH E 2;: DH S M: 2 HN mm %N WN %N 8 - - - I I I I - I - I - I a DH a DH a a a of: DH a a DH a a EA: mg WO 64460 mzz mzz mzz mzz E N m w m o h w a : S .3 E EE E E .ch E .20 hm .qu E .ch E .ch E .ch E .25 E .ch hm .ch OHM. E .30 E .20 E mo 52% £6: DEN an: m am 5m 6-0 Em. - 5 N :3 Em-m :2 a": :2 as: Em-m E - 2- N an: mm m E m E m m E m m m m m E m m m m E m E m m m m E m m m m m E m m m m R £000 HE000 "mooo 5000 m m E m m m m m E m m m m N: 2 E m m m m E m m m m 2 E 2 n m m B m E m m m m E m m m £0 £0 mEU £0 no m m ¢ 020-0 020-0 D O an 6% 5% flameI WowI £90 £90 £06 £90 6-0 6-0 6-0 :3 56 6-0 6 5 - - c o :2 .oz mm om Q 3 - - - - a n: SA: NE 8;: EA: mmAfi 0?: EA: wmé of: 9i: El: NE: a a 91: WO 64460 .3 .20 E E mS/ E "9/ E $7 E $7 E $7 E 37 E $7 E mS/ EW/ "EM/Ex E $7 E $7 E $7 E 37 E mS/ E m N m am mEoN E0 E 6 «H 6 «H E E E - - - m - m - I 5 - N N 02 I - N N E0 EN VE N - N 6N - N N 6N N - N mEoN N mm m m m m m m m m m m m m m m m m m E m m m m m m m m m m m m m m m m m an m m m m m m m m m m m m m m m m m R m m m m m m m m m m m m m m m m m B m m m m m m m m m m m m m m m m m an 6-? £0£o£o¢ 6-? £90 6-? £90 6-? £06 6+ £90 6-? £90 6+ ago 6-? £90 6-? «Ego 6-0 6-0 6-? £06 6-? £90 6N $0-0 SN ago SN £90 6N .oz £1: E w? 9" cm E Nm wmm 1% E mm mm 8 6 - - - - - I - - - I - - - a a a a a a a a Kg: Ewe a a a a a N3: A30 A38 AS: ENS 53 A8,: £08 five AS: 89: as? Sww.mx$.833.138 53 .3 E? E E? E E? MW/ E "9/ mW/ MW/ mW/ "HM/Hz E E? "mm/Hz five mEx: "£on 55$39AAmwswvowovmévma 82V x8: owmdm $8.0- m :3: 083 £3,138 2&3 am "6 - E E 2 E "E E 6-N £5 E vi "E MR: wave N A50 A89 A8: am? o8: 33.125; ABMs; 203 88.0- 3&3 mm m m m m m m E m m m oExo-Z-oq%E\a A38 $53 mane 33éqeoooqfiaod 952 £0: A2: 38w "5.9; 88.0 83w v @on E m m m m m m m m m m mams m2? A33 x38 6088386 Emma SSW Roms 52 so; Ho: $98 mamas; A38 RE: R m m m m m m m m m m soungswmsoo Ezmadam $3 32 22: Show mam: £on wmmm.mxovo:$m.w A33 Nmzmagm fits 930an N: m m m m m m m m m m mm Raw so:x383313858913023.» :2; 83mAmweommoamaveomgficwe @on 53 mpg "$832:st x38 mam: 5:8 five 5:88.865 5m: B m m m m m m m m m m 859 ma; 8%.» SN} SN? 83w m Nemzn-_wav Em: A3,: A03: chfixpdéfiom mews Naggvav mew: an 5-0 6-~ 5-0 5N 5-0 FE 6 6 - - wowfiw 9:"? 29% mamaAmacofioaxmm: mauve New? $86 o 6-0 6¢ 5-0 6-0 o 5-0 anbm 5528 5528 mam: £2; Amos meme fine 0SA: a1: .oz me we 8 E - - - - a a moé a $-a mi: of: owe a a; "($885on 52 $0; Nmmms mg? $8.13: 3513.8 Ema 52 38.0 A38 588530.128can: as»: 88.0- A88 m5.8 A885? 8:; $025868$3.13.:vow?A3888amcmdvfigméwovokoaéwov83:38Sadie:28.138ammoaxmodfimoaANN: aw: 5:: 808 38m M38 A38 A38 CONE A38 A38 Rafi A38 $88 032 #32 £33 8:; A8,: mmooaxadvomga A38 $8.0- 283 m80.8 331%.8 $0188 52 Saws $30138 203508 A28 Amw8fio§ ~83 83+ M: Awm8 .033 m8:8 5W8 A38 flood A828 588 x888 mew: as; 538 A38 333 063 A58 5:: A818 £8 $3 AR: ommow 593 3va £38 m8? $03 EM: E3 $313.8 53 $28 88.0- RMESRQ $82 mom: So: A38 5? Em: @08 So? m5.8 mam: x88 £28 53 x28 AS8038 598 58 Sm:Amwovigmxmmdv £38 A8»: AS8025 53 A38 A38 x88: 0E: $2; mommmévmmv A3838.0$882.18.: A8,: Sq; am: 28% mcodfiwoafiw: 933 A38 figs A3: 5:3 80.28303 AS: 38.0 $8.138 x38 03: A88 355 0%: $33 5&8 083 Mafia mag $02 mew: A28 5:8 083 888 A28 A598 A38 A38 2:: 35m 858 33m 588 598 Em: 0%; A38 3m; 3K: 33 $88 23.138 5E8 A218 893 AS: 8&3 $6.138 58.08183 3%? womoigd £58mAmwovagmA38OR;A3885m€0.5882.18.8830? men: 302 Awm.m8§@.m 8%? NE: $03 W898 28¢ @98 A38 A908 $8.13.: 38% m80.8 0.83 A38 58.8 A8: 0;: A58 AS: £28 382 $8 m6; New: $03 $02x38Mam?50.8R§.Ném8802"30.88318:38.38.8033 8&3 #8": 5:8 A38 $me Ewfiavov $38 8%.» Ambomvamom.mém.§ A858 $3.0 EM: £98 2me 083 WE? m858 38¢ mam: x3: x3052? $2.13.: mac: 89% 231028 x8159; ":98 68: mA38 A2,: A888 02 $3.188 082 888 5:80;? $53 m3.8 m$0.8 x38 dmmmmaxmo: A8,: 83w ma: $88 am 588 28¢ 83.0 208m A388 8:; $58 833 NEE £28 33 A83 A38 588 maméwov82.18.8825A38 828 ma:850833N£Qm8$312.58gowmmeommvomam mewssgw $8 :fi: A88 A8»: 838 swam $2 558 mam: :83 £58 A88 2%.188 N82 A28 3%? Ezmadmm am; M83 33:38 $8.188 :38 33 838 803 A38 in: #88 Sm: mA38 353828 893 was £38 $8; m5.8 A88 5%.: 88.138 Nmzmadam A38 858 5%: 383 $~w~ Nmzmmdam A3,: mam: 5%.: SEN Nmzmmdmm £38 AR: 2001808 $02 Egmqamm fins $03 83: 8m: 5:88:on mom; 533 52A388£250.033.18.28$5M 5:88.865 38¢ 888 :53 :88 :5me 838 03.3 m:m8 R313: $88 m8? 083 83188 538 $03 M888 A88 m$8 £8,896; £88 £2 x28 A38 803 Ezagsam §M8$Ri$8 88.288 80.: £88 E3138 8mg 883 "5:88.865 m80.8 x38 m:08 EN? §3 gaseogam 53.8 3wa Ex: SQ.1E.8 Meme/chav N2: 58 _wav 888 083 A38 nAge/Hawvav $88 as": EBB" A38 £28 2:; Em? A8,: A28 9%; A8: A38 mmtfiavovmfiwmx388 8:333 A8,: 832 A2,: 588 ME; £3 2&8 mam: 58.8 A88 $8M 80.8 Name/chav AWN: A38 $8.138 3:; 3N3 :28 wvav A3,: wmnmw 88; 88.138 A2,: Em: £28 55:8 552cm 3%; wow: $8.138 A28 38.0- €528 EN; Em? ma: £08 38.0. 8:3 A88 508 38.0- Eng 5: A28 £08 38.0. 552cm 55:8 m5»: 5&8 88% A28 53 A58 528 A008 A38 m5; A328 5%.; $8 $3.138 083 £38 5%.: 538 fa: m:38 61: 383 REA: 5;: 33 4?: 83w :88 op: .cz NS? 3:: 52 was; 3o: E? 82883138 A38 88.0 52 ME; QR.» 883 53.8 3%.Nxmm838.128 88.0 .2 £38 28: $8.? A38 50.8 88.0 52 $03 2012/071385 %.: 2%? 55:: 53.: m5%.: 331%.: m5%.: 5%.: mac: W3.: 5%.: 5%.: m6:: mA+%.: 5%.: 58.: 23% 9:2 335%.: 88% 5+: 82% 53.: $03 £5: 88:- 5%: wow? :82 GE: as: 33% 5:3: of: 5%: €03 :02 53.: 53.: 0%? +: m:%%.% mGo: m8+: 5%.: 28.18.: £2: 53+: 55.: 50%.: :82 5%.: 5%.: 53.: man: 5mm: 5%.: 38.1%.: $2.15.: +23 8+2 58+: 58+ 58.: 8%: 8+3 %O%%.N 2%: N2: 88% 53: :3? oomflmmam: 28s $5.» SR.» 0+0: 053+ 82+ 5:: m6%.: 38.: $3.18.: +.:8$+éo.: 63% 5+: 53.: 5%.:33+559038913: 590.1%: M5%.: 58.: M5%.: mam: :52 5%.: 5%.: 5%.: mega: 030% %+.: mwoo.% 53%: 5%: $5.15.: 32 $3: +5: 38% 5%.: 88s 05+: £3 +©+%.% 351%.3 ER: m3+.:o+%++ .+ 53%: mama 58.: +0: %»: 3%.: 50% £QO53:33:15.: 5%.: 22% 52.: WAG: 55.0: 5%»: mA3: 58.: 58.0: 53.: 5+: 5R: 28% 82+ :3: $8.13.: 58.: $3.13.: 3313+: m3? 8:: as? %.: 5%.: %.: as: 08+: 5%: 55% 33.13%: 2%: ME: m$0.: $3.103: 38.0- %.: 5%.: 53.: 5:: 0:3"89:85.13:$313.:$358.: 022 9%.: %.: 831%.: $2 5%.: 53: 58.: 5Q: 850.1%:$5355:Sm:5%.:+53%fiooigfieb: $on 5%.: 5+: +%2+5%.: WSWN 503: 58% $8.? 23+ O%%%.N N83 o+$+ i2 0:3 $3.» so? 5%.: +83 5+.» +23 83% 53¢: ma: 83.» +o+5+ 53: 88.0- W80.: +55:38.13: 53: 02 $313: 58%: 53.: 32.28%: éw:%$+5v: £318.:53:3:$0253.:RSNAQ:mmmwfipw: 5%.:: 56.: m5:: mA++.: 53.1%m.:$+o.%58.: SE 58.: mso: 5?: 5+: 5S: 53.: w+o+N ms? $2.26.: 33% Sm? 0:: 86+ 5%.: 88:- 2%? 2%: 08%.: oE%+ +8353: 5%.: $3583 $8.186: 38.: %.: $5358.: 53+: 53.: 5%.: 5%.: 5%.: $85 W3.: :35: 55.: 5K: 5%.: 50+: mg: 5%.: m6+.:Nm$+ma%.: 55+: 53% E2553 0+3: 300+ 23.1%.: Nmzmagm 2+3 SN: 580.13.:E3552: 5.0% 53.: 38.: $2353 :83 3%: +3: $0:mew:+8w.mmaw.: :83 +32 83+ :+w8.%53:02:28.: Rm: 53.: m5: 5%.: 5%.: 5%.: 38% 5%.: m:9: 5%.: m3+: N%m%.m5:.:@%o.~ Nmzmagm 50.: 5%.: 5%.: 5%.12.:+O~%.~ 5%.: Nmzmmdmm 2%.» $0253.: $313+: 55% 2%.» S++.% @8013: "Emagsam 5:55am 5+3 R+E 88% 5%.: E2 "5:88.865 88% 8+: 2+3 +©.:+8913: ommwaéw: 58.: 5 "5:88.865 $8: 2%? 2+3 mam58.:+%2.%AN+.: m$0.: 2%: :: 558: 5:3 5%.: 53.: mam: $02 6%.: 5%.: m5%.: 5%.: 53% m6%.: mA%+.: 5%.: 5%.: a: 53.: 5%.: 5 3: massesaam E: 8+? $5558:35.13: 53%: nAo.u§n._§v $8: Na? NN%+.% 58%: +890- NOE/5-3V $8.: 8+: %%+o+ 33% mA++.: 8%? Naggvav £8: N32 M63: 58+ $5,100,018? EENAQ: $8.0- .AOmzn-_wav $8.: 2+: mag??? So: 50.: m9+: +83 m6%.: m5.: 55.0: ~22 5:3: 5W+.: m9+: mAS: 5%.: Eva Ami: mA+%.: 5%.: m@N: m5.: 83% m5%: 5%.: 5%.: 58.: 52 %%N%.m5@.:-+%.m 53.: NOwSQvEV mom: 33% mGS: 552cm +23 N33 88% m3+: 88.0- €528 +53% 3%: 33+ 83% 50%.: 5%? 5528 363w £2 2%: m+$+ 5:: 5+: 88.0- 552cm 3+3 3+: W5%.: 5%.: 022 58:: "25:8 %.: 5mm wag 8%.: 5%.: 50.: 5%.: 8+2 wag m8:: mA++.: 5%.: 5+: 5%.:: 33% £3: 5%.: WAS: 5%.: 5:+.: 38% 5%.: 5%.: 5%.: 53.1%.: 23% 5%.: ?: n2;: +3: £5: 6?: 3+3 +63 5%.: 5K: 38.0. 52 38.0 we: 33% m6%.: m5%.: 080.: 52 $3M: 8%: 83+ ow+%.% 55%.: 83% 52 33% :23 6%.» %%%©+ W3.: £8.13: 98.0 .2 as; 5%? 33+ 33%5%.E:+:%.%58:2»?5mm:wagx%+.:53%55.0:owg.%5+%.:m+oo%5%.:88.13:Emoifiw:+w8+ 5%.: $8.18: :32 .oz 58.8 588 58.8 888 58.: 58.8 888 58.8 588888588 8+8 58.8: 5858 58.8 5m+8 58.8 58.8 588 588 58.8: 888- 888 58+: 58.8 5?: 88: 88+ 883588 5+8: 58.88 88:58.8 888 888 888 885 $88 +8: 88+ 388 88: 8+? 88.188 :88 5m+8 88: 88: 888 58.: 588 8 5+m8 58.8 5.8 58.8 583 58.: 588 8:8 EN 58.8 58.8: 588 58.8 58.8 58.: 588 8+8 582 58.8 58.8 588 a: 888+ 88+ 58.8 28.» 88+ 888 888 +83. 8+: 888+ 88+ 888 58.8: 88.8 883 588 m++2 888 38.5 3+2 88+ 888 +8: 58.8 58.5 88.» 88+.» 8+888.18.8883 88+ +m: 5w+8 58.: 8888 58:88.853:83:88 58.8888+58.888.18.88 88 58.88 58.8 5+.n8 588 88.8 58+: 588 m8; 58+: 58.8: 58.: 58.: 588 58.8 58.8 58.: 58.8 588 +8.» 88+ : 58+: 8+3 88.8- 8m: 88+ mm:+5+w.8 .288 58.8: +8: 888 +83 +m8 58: 88.8 8mg 88+ 88.8 8+8 58.8: 8+8.» NS: 28+ 88+ 58.8 8+8 588 5+8: 882 58.8 588 58.8 58.8 8+; 88.8 58.8 58.8 8:2 5%.: 58.: 588 58.8 88.58. 58+: 8+8 588 58.: 58: 588 88358.8 889m 58.8: 883 +83 88.188 m+8+58.: 5:8: 88.5 88.8 E: +8: 58.8 :8; 3+5 882 888 5:88 88.» 88: 88+ 85 55+.8 888 58.: 882 588 58+: 58.: 58.8 88.18.: 2:8 588 58.8 832 52+: 58+: 5:: 58.8 58.88 88.8- 58+: 58.8 5:8 58.8 88.5 88+ 88+5+w:+m:+5mb8 8+? 588 888 88+ 88+ 828 588+: 88: 83.5 +E+ 82+ 882 58.8 88.5 8+3 88.5 888 82 883 $88 58.: +88.» 88.5 88+ 588 58.8 53.8 5m+8 8:3 58.8 58.8888 588 58.: 5:: 8:3 58.8 58.8 588 588 38.8 58.8 58.8 58.: 588 58.5 88.8 588 552: 588 888 88.8 888 588 88+ 88+5888:+ £28 58.8 mm: 88.8 +8; 58:83.18: +818 58.8 8+8; 88.8 88.18888+58,888+58,888.18: 88858.8:88858.835+58885.18:82+58.88918882.18.:82.18882.188 +82 885 888 888 8st 58+: 28.8 3+: 58.8 58.8 588: 88.8 58:88.8 588 58+.8 58.8 3+2 58.: 588 5m+8 888 52+: 58.8 5:8 58.8 58.8 5888 88: 58.8 5++8 88.188 58.88 88: 888 88.18882+588883588 +888 588 $88 88+ 883 58.8 88: +888 88+ 5w+8 888 8wa SN: 883 8Ea 58.8 88.8 +8: 88+ 8+3 58.8 58.8 58.: 888 £28.88 £23.88 83.18.: 828 E2888 58:88; 5++8 58.: 588 8+3 58.8 58.8 5m+8 58.8 888 58.8 58.8 58.: 58.8 58.8 882 523.88 58.8 58.8 5m+8 5R8 888 58.8: 888 :88 58.8 "5:88:98 28.188 88+ +82 588 8+8; 5888825 88.8 88+ 82+ 888 58.8 888 5:88.88 88.8 88.5 88: :88 852 555+: 8+3 8%: 8:+ 88+.m 58.8 58.: 5+N.m: 888 888 58.: 58.885; 58.:82+58.883.18.88 58.8 E88 58.8 5+2: 588 588 53.88 88.8 5m+8 58.8 58.: 5mm: 58.8 58.8 88.5 "5:88.855 58.8 58.8 58.8 58.: 888 88.8 E? 588 58.8: +888- v SN: 883 588 8me n65887—55 88.8 88.8 82+ 388 5m+8 888 8+3 2+: 88: 8+3 388 58.8 88.8 88: 88.8 +888 58.: 5:8 58.: +888 +8+.~ 585+: 58:82.18: 5:: 58.8: 8:3 58.8 5+m: 588 58.8 52.: 88.8 5888 Kawasavav 58.: 58.: 58.: 58.8 58.8 38.5 Nemzn-_wav 58.: 58.: 5+8: 58.8: 88.8 8:: 88+ 888 588 5:8: 88.8- "25:8 8+: 888 588 888 5528 32.8 M88: 82+ 888 58.8 888 58.8 55:8 88.8 8+: 88.8 22+ 828 3+2 58.8 5528 88.8 88: 3: 8888 :: 58.8 588 58.8 888 883 58.: 58.: 58.8 .85: +888 58.8 58.: 5:: 5+m8 58.8: 888 58+8 +8.8. 58.: 588 58.: 5++8 58.88 53.8 5;: 8A: ++8.N 58.: 8+8 5+8 "8-5: 8A: 888 :8.» 88+ 88+ 58.8 5838 88.8 .2 88; +88: 83+ 888 58.8 :88 52 +8; mm: 88+ 888 58.8 888 58.88 .2 E88 88: 88.5 88+ +83 885 58.8 52 88.8 +8: 888 82.18888.18.:$2.18883+58.888353.8Smm+5++88+3 888 0:3 A35 wwwop 5&5 5:35 55.5 ":95 83 EN: 5:65 monmd 50.5 Emma 5&5 5.8.5 ":95 5:5 at; 5&8 "C05 wooed- %.5 mama BEN 32; $93 555 SN? 52% 55.35 5R5 "awe 55.5 53.8 5&8 535 823 Sod ENE mama 293 "855 "858 5&5 Eonm mwoqo- 5&5 Sm? $55 38; 33 mmomp 535 52% $85 Nvmmkm 89% name "5.585.133$85"?de 56.5 "6:5 its "£35 Sum; ES £39 :38 $3 "8.5 885 SE; 885 "3.85 8m: "$0.5 "60.5 5&5 52$ 53.5 55.5 $.05 ":35 "C39 &5 285 NEE A mmomg "Amos fiqmmv 5&5 8va mood mammd 33 80mg £85 55.55 8.5 8va 8N3 N83 5&5 5va RN30, 5535 £313.05 $58 053 55 "fine N82 &8 NEN 88.0. «3% "8.5 5345 5%.me :55 "C5 flood 83 833 58.5 "635 55.5 535 good. 56.9 mama; "no.5 202 5w. 5:.5 5mg "fine 83.0 $93 Swim Hams 9:? 55.5 "awe mtmg 55.9 5 x35 Emma Sim £3 325 "635 Eonw 28.0 553 BEN "3&5 Em." NwNE 855 5:35 8:2 5505 mam? $85 "8de $8.138 Amos x3 3:3 $8; 5&5 #3 Em: "8:5 "€va 535 "C35 5x5 "£0505 ":98 5&3 ":55 55.85 33 mommp "635 55 "3:5 "6.8 mm? N83 N83 886. 538 x89 60.5 3m? 5:85 5‘de $5; mfimkm 22$ 8%." 5N3 "A Hams 85." 8:." BNQN x565 momma Scam 5%. £313.05 53.5 5‘35 5 $5 2mg ENQN "£95 9:3 5 803 5558 x86 3+5 «52 vwmd 82% 55 55.05 53.5 28.0 £55 5:5 "6.015 SNQN 5&9 x85 55:5 at; smmameme 38.0. 5&5 good "3.5 25p woomkm "$95 8%." Mane 55.05 5&5 80? 5:35 83 5035 EVE 5&5 5&5 5:35Sidxamémwood- $85 N03 32 ~83 5:35 85 M83 £36, SEN 83; 5&5 A85 88p $2 "awe Envmémegmoa "335 SNQN "65 NEE 88+ E5185 Efi x55 535 555 "5. 50.5 "825 NEE 555 5%. "88 Sam 5:5 5%. 88.0- 56.5 "@255 8an good. 5 S 5 "85$ ":35 5 $3103539AA355oweséwigmowmfiwé98.13.25 m: m8: $.05 N8? 5%. 855 $26 5;..5 "$35 "fine «85 88d 836 82 8%.», NE; $85 EN "60.95 :3 5&3 mam: 5 5‘de "fine among 38d :8; fits 535 55.5 5555 5:35 55.8 «83 585 38+ 58d "$.8588.95.5805 New: "Cd "8905 ":35 "no.5 55.8 "6:5 33; "awe 53.5 555 53.0- 5&9 "so. Reva NS? "65 "£95 5:35 8&5 AS9033 88.0 am EEN 88w 5E5 555 mmmtw "$.05 flange Nmzmmdmm 55 5Nmzmmgm mm? $55 SEN 88.0- Nmzmmdmm 5:3 among $55 $55 Nmzmmdmm 85.x :86 5&3 52.5 5508 mats 52353 F; 88% 885 ":35 55.5 5&5 "Ex 3 :8." in "80.5 2&3 385 88; "5.8 "A5 "8N5 5555 5&5 "36.5 5%.
Ezagsam me5 Swim 2838.865 5 $8; ":35 "3N5 "Same «Sim mwood- "E55 55 "£de "assobuoam 55. $3." "3:88.865 5K5 "$0.5 56.8 $8; 55.5 03: 85¢ 5N5 $35 25% name 5 «RE wow: 853 28.0 885 $03 885 tumnm 535 Execssam 855 ":65 mmmmkw "3.5 EmE mama "8N3 fimmw 853 82d 88K "335 38m 5035 5535 55.5 3N? "$de 8qu "@1883 29¢ ":35 5N5 58.8 5:5 5&5 55va 5&8 505 "5.85 €th 5&5 wooed- 55th8% 52.5 "8.5 an? "Cod "€15 "$5 $8.185 "Eye wmmnm A8580? to: nAge/H.555 "New 555 wmoqm 835 "flame "335 533 85w 5&5 $86 5%me 29; maid 85." 88.0 585 5&8 885 52.5 SE vwmd "$5.5 v33 So: Emmg EEN 538 x35 SSE 55.55 Newsagvav 53.18.5385"Amoflimwod n: Emma Etm nAqua/H.555 "c. B: "$95 "$.05 55de NOwSQvEV 5‘an "655 5&5 "658 ,Aomzn-_wav 2:3 "5.5 "as "6N5 5565 wood .3V 55.5 "625 "flog "£95 Agofima m3: "695 $55 mama "CmgvfimZ 55 ":q 5 NVNQN mwmnm 5528 god "6mg :5 Emma "855 $23 53 St; gum; vmmog am; SEN 53.8 $53 $2} 38.5 885 "A535 836 252 Saws 88.x, "A535 :1: 5%. $5; "$0.55 "638 5528 wow: "25:8 "25:8 552cm "252cm ":55 x5 ~83 mafia "35 EN: 535 £55 5:35 555 ":35 "fine "608 $3 "605 555 535 55.85 835 "$55 ":25 "635 A51: r £1: A91: 5?: 4T: $5: 5525 83 52.5 mm: 5 52 Ed "$5 mmmnm $03 2: .2 2&3 ":05 "Amie .2 E3 5&9 SN? named 50,2; .oz gig ENE kag $$d mane .2 Saw 825 855 onN "ate 52 8% ENE Sow." Rod 535 3g Kama Foam SEN - Maw» moo: "flog "ammo #5 Noooo- "635 ":55 "$35 55 $35 "6oo5 "8352.135 Ammoo 2R. NNmE Ramos "$95 "and mvwoo x368 omoE 58.5 SEN 98g Sooo Nomi Haws coon." "$35 mane Smog SEN mos} Roam, 9% oooop Noam moooo- "ammo x855 Noooo- oootm "3.5 goo momma Eooo moo": "$me "88 oomm.m Eooo "655 "65 ":35 "Cooo "goo room." "Ammo 525 £25 "€qu "code EV: 89g "655 good. No3 mmood 9;? :83 "60.5 "€35 EEK "Anode woo; "Cos "goo 82; go: $9? flood Ronm "ammo 3mg "825 "rm. moo: NEE ":95 "Amoem5 oooo "coda "8de ":35 Rm." 5 x85 ":35 "698 moooo- 2:3 :22 "695 #95 "amino momod "ans S26 good $85 553 "Amado xoog "835 mom: Eomd "Ammoo mooop voNQN ENE ":95 "too "6.5 oft." woos 52.85 $3; "sod "aoooo ammo mom: oooog Noooo- 535 Sam "8o. "835 "ammo mom? 5 $3} woo? $qu mom." BEN 32% "€35 Now? 3%? Sonm "895 "Cooov xoooo good 5 Hams oooooo ":ooo $va "695 "6N9 onooo 3N3 "6N5 "6on 9&3 "ammo "ate ooooo- "some Smog 55 x38 ":35 x35 5&5 "$35 "Ede ES 23m Foonm mmooo ES "8on okooo 5mg Koo "6.8 more; ENQN "$35 omoE 983 owe} or "8N9 "635 "6925 NE: 5o." $55 omv: E? ooomg $5M Koo." 8on EN "835 "an? "ammo mm." "cod "$6.5 "695 "658 893 ":oé "899 "Ema Foo: Smog Mane mood Emma ":35 one? "cog "$35 omoo "835 Noooo- x25 "655 x365 Hate "om? too." "$58 "ammo Am}: oNvQN vomod "$35 "65 good moonm Fmoog "85 ovmwa "35 mom: "6qu 5 oooE «No: ooomg ":35 x25 8N." N83 SE to: "rod 5% 2&3 woo: oooog #95 "3&5 "gov x85 good wooog "$55 "A88 "6535 mo: "$on "695 "Ems "£on oootm "ammo Rmoo "€55 mmpmo oomo.m Rooo "A235 «2? "€35 "325 ":5 "658 :8." inoo "@on "$35 oommg 35m RN? mono." "8&5 Sid "8.5 8%; "8.9 mot." "835 "6085 8o: 2&2 ooomp omood "Amooo mmomm on? No: 85% flog flop "858 "rod "8qu mama ofimoo "cog 83." go? "some ovom; B. ":35 "Amos :85 65 Nmmooo omo.m "635 "8.8 "639 "E55 éooo "sooo $5 megs "3.8 5.9 Nmzmooom :omom om Soto 5 885 E2353. $3 5N8 Ezmooom 3:: EN? MaooV oood omo: 6.5 "A335 $5 Nootm 33o 2: "an moo: "835 gm: Rood 51m"$358355&553ém.m5 Hams $3 SEN "some "Amoov 38; room." ":35 ooooom "335 momma Nmzmooom to"am. "ans Nmoomooom Nomto Kooks ooom.o x2. oovoo "$35 E5 "$35 "30.5 x85 "635 "855 "ate "8:8 oovwg mopod "ammo :5 Nmzmooom ":95 5 "Ame 55.5 "EoEoEoom ooooo :osaobooom flotm mmomd Soto moon», :Boaobooam ooooo 3: "$35 cesaobooom flood ENE 88." "Aooov v83 "3:883on mooto "6.5 "8qu swam "655 5o? ooomd 835 88o EEK &5 892 "835 Eotm Ed 3.5 mooooo 5o. "835 £5 "3N9 "cos "855 momma, 535 amnm "rod "635 "ammo 85% BEN "goo "hoooaobooam "8» moo: maoooo "653 5:88.865 "A #98 5.5 ":35 Cmoo ,Aomznfiav 5 RE "soé Eood Nazavav Road Noam oootm nAcme/vaav ago 2 "£5 "3.85 5 x35 Roi EN Nemznéav 82.x $3." "A935 85o now: Bomm nA9¥fi_._§v mono x35 momm.m wood "635 $3 $5; $5." 83o- "808 Sonm Mane Kmoofi 56.5 "6on "635 "soomo Hams ":59 ":35 noovo Sonm "so.
Q "6.3 68.9 "$35 "65 oooo.m 5 o3: oozd ":qu nAoflflznéav ":35 5: #35 A865 Nemznéav "895 "$95 "Gog 83 Noam €95 5528 5&5 5528 8:3 N9: homo flood 55:8 oommo oooog "Cm"F5 "6:5 moooo- 5528 voowo Foo: Smog 885 Nooonm "335 ommmo mane ooooo- «wood- 3:3 Amado ENE 53 KNEW worms "85 x855 flood Noomd "$.95 "25:8 "no.5 omoo.m 55:8 5528 flog "635 xv. "and "cos "835 "rod "65m "Ammo "63 5; good of: 5 if: 5 nmmo: 0of: Mao» Foo: "635 Mao» VVVV "3N5 oomi 5 5 "Amos "ANNE "smog 55 REA: homo: $5: .oz flood "a5 SEN "838 52 good NNE 88.», omomd .oz 35o 85K ":25 "soda Noooo .oz 39% moi." ommop Emma, SEN "33? 52 ommmo ":85 Roma"Ems8.18.8386"C382;x8535;5&5 wood "835 aoov moooo- "flog mmofi .oz oomoo "Coke Now? vmmmd 52 moo; ENE Ego Rood ooooo- "an oEE 55.83 "Amos 56.8 moms oomoo omova moooo- goo." - mats "623 "E3 F3 52.33 Nooo.o- momma, mummy x53 wood "833 "Cod "£33 "633 xmmdg wood "$.23 55.8 58.3 533 "CE: ovooo 3 "838 Eono 533 food Emmi xmodoo 5383 38+ Sonm 3 «ES $62 :3Mani53.133335 "€33 5:.o3 FNVNN "8on NE: Koo." ooooo E: Emma 5%.? 88.? «$3 NS; "839 ":93 3N3 omom.m Nooo.o- Ewe "633 "633 oooo «wood 5:53 $33 "633 Soim Noooo- "633 5323 "5.83 fog 55.33 "Co. 53.8 58.8 Bow; 5&8 ":933 $35 So; gone 55.83 oooog or "flooov memo." "$53 woos oomoé 5va xo.m~3 "5N3 good «RE Noood &3 more." Foo $3 woo? 53.8 Ego." to? «mood 5%. 285 voomo Sooo "$33 56.9 55.3 ooom.m oNooo "$33 53.3 33.3 Bow; xo.o3 :.o3 good ":33 53.5% 8%; 55.9 ooo.o 52.3 3 oBoK woos "$qu 285 "6on %. 5&8 5:53 St; "C93 "$33 "833 okoo 5&8 58.5" 235 Eovd "soda "638 N38." oooop "638 5853 name 59% "3.83 3 SEN $5." xmm. ooom.o 3 So." homo 3 oovma 55.3 éoov 5xo3 xom.o:ooo.m Room; "3o.o3 ES BEN ":33 tom; SEK ooood oomm; 33g ":on 5E3 55 EN "623 ooom.o oomm; "C39 53 moonm 53 58.3 55.83 82; "823 x3 58; goo." Emmm 885 "833 omoé Boos "no.8 5:53 "6on "Ammov oz"? moi." Emoo 5N3 owomp 5353 EN? £38 835 "$33 "no.3 5%de moo: mm? 59% "co. ~85 "6o. 88o oomm; "Coo 58.8 "3on 5&3 "@323 "6on mom; 5V3 mm.m 5:83 $56, £33 SE; "Cooo :53 8%; 3on :3 32% 5553 56.9 55.8 "833 "633 3 "6.3 EE ogoo "6393 Room; "6o.o3 6.3 "foo $on Nvoop :3 5:.8 omoog «mood "5.3 ":33 flood oomop So: 53.8 585 gone 89% NE? "3.3 NNvoo out ooom.m "3o. 55.3 3 $33 3N3 Sow; 56.8 5&3 "6.8 $3 Mame momma, ENQN "wow; EN? 5:.8 woman $3 flood xoo.o3 "foo 825 $55 5&9 ":ro 855 55. 58.3 58.3 Boo "Ame room; 55.8 "ate oovop gown moo? BEN 53.8 vmmog xooov 28o "3:3 "833 "8N3 3 3N3 55.3 "6.3 moood ooovg 55.8 on: win." "Amos EEK oomo.m Sooo E2." 55.83 SEN 506.9 28o 585 moo? 5&8 53.8 "cog "flog 885 xmo.o3 855 "6.0.3 «mood 5&3 So: 3&3 ":23 5;. ENQN ooomg 5".o3 moi." 55.3 fine 3va 5&3 ooo; 55.8 oz: top ovoo or "633 "Amoov "Amoov oo; :33 ":33 to 533 Hana oomoo :55 ovmod Nmzmooom "$33 5o.o3 55.8 ":33 Nmzmooom E2353 2N; "flog F woo: mom? "833 8N: "3qu 5.6.8 $55 Nmzmooom flood oooo.m E2353. too 58% moo? SEN "Aooov 56.3 ooomg SEN "3&3 Roi 5:.me Rondo "3on :56 385 58; omovg 533 "Aooov 5.3 5:5 553 855 5&3 "699 Rooov "5:82:on mom; 23¢ mmog voooo :BEEUEm 53o "$33 Em; 5&3 bag :BoEoEEm ":38 omooo "6on obi Boo; "Cog "€qu "an. 5:88.865 5%.3 855 "33838550. $36 :5ng oooE orooo 5W3 53.3 3 woo; 3N3 56.8 533 "ANN. 55.33 "6o. woos $55 owod "Cos 56.8 F3 5%.3 $33 mow: Nomoo BE "Amos 5&3 "Ewe good :3 momma N23 "A83 #85 "633 "333 "8&3 F "5.8 momma 5&3 3 Nvmod "Amoov Nazavav flood 50,3 53.3 5:63 Somd EN: EN? oEoo .AOmzn-_év 22% "853 55.8 x563 5V ooEo 53% oooog "Aooov "6.8 name Naggvav flood 55.3 oRoo omo§ .AOmEQ-_§v SS "wows moi." 255 885 "€33 :. "63: Bog ogoo $85 "8.3 5mg r "Code 3 ":33 E: mm; Noooo 55.23 83$ "833 5:33 5me 855 3 Noon." good NS; "8333 "ANNNF ":33 gone 5.3 "8o.53 éoov &3 oomo.m x33 ":33 "363 "25:8 $56 moo: $85 fioo 2on5 58.3 55:8 55.3 "awe 835 $2} 559 mwooo- €528 $36 omoog So: "gov 5:33 "823 "flog Nioo 3 omooo BE Koo: oooo.o mooo.m "coov MES Food $35 ":23 "Ammo "Goo 56+ "goo moooo- "ANS 23¢ mots mooo.o good "$.83 "25:8 "2528 Boos, VVVV "5523 563 533 ":33 Fommg oNooN "83 Smog 53.3 5V6 553 53 "ABS "a; "a; .85: 4?: .85: .85: $5: VVVV$85 "awe 533 538 Co.3 .oz 88o 89% N32 voooo moomd 56.53 .oz moooo 5:83 "633 "8me 22% Noooo- .oz moooo Koo." flows ":33 "$.23 "3N3 a.3 .oz Nomoo 53.9 oooo.o «3318.83 moooo 52 $33 Bag 3o? good EQN 58.8 moo? oomo.m moom.m 55o" 5585 5R8 "835 9:3 5 58.5 88d omFS oF F Fe mmoqm Foood Noooo- F55 moo; momma 56.5 52.5 #35 "gov "$5 "65 ":ooomv good5 Food momtm oooog 55.9 5535 555 535 52x5 "£95 58.8 moo? vootw FFom.F Rs #83 ooFQN $42 8on 83% 56.85 "335 55th "ANFNV "€55 25p "658 &8 8:; Nomi REF $26 "ANN. Noam 5% 55.5 &5 555 "$59 F22 woman 55.9 5&5 ooFm.N was wow; 88d Rood Foo: 5&8 omNmN 5o. Mamie Hake 555 5}: "€35 "6.5 ooomg $55 55% 83 ooFooN mood 5555 ":5 55qu 56.5 5:85 «moi 5 93 own? 35% FooE 835 Noam SNQN "so. "at 5:.3 5555 58.5 "8:5 ooFmoF "85on "$on Fooog Fmomg "Cmomo Foo; oNoFfi "$99 name "8355 "8.5 F 55 woo: 5mg moooom oovod EmNF "$35 &5 ommo.m «23 "C55 52.5 5535 oomo.m Evoo "Ami "$58 5&9 55.5 oFmK "€35 Noono "6on moan F3: FEE "Gog ":58 ooooo N33 ooomg FoFoo 89% ooomg momma «N3 oomo.m ":55 56.25 "Cm. 55.8 "flog "sod "£35 oommg "5.85 NomNF "A 5555 "8.5 F SE ooFQN moo? 5ooood 5&3 momnm ommoo 285 5%.5 Fmotm 5&5 5:65 "8on Foe ":5 5535 mom." ooomg "855 55.89 &5 mm? "5.5 mom: $3 5on5 x85 Mame $5; good 95% «moms momdxow.omvfiom_m"€358.50, 5&5 "flog omooom FEoo moons "$35 wot}, "855 55.3 ooom.m "5.8 "€55 53.85 xmo. mooooF 5&8 $2 So: 55.5 &5 «33 "Ammooov $03 5K5 56.5 "$35 ":55 56.5 "£5 "AFoov 58.5 F Foam «mood 5&8 8v? ooE 535 oRQN $va 5;.5 moo: mom: good FEN "6qu ":99 "Coov Eotm 5:55 5&3 "E55 "@qu "655 38K ooooo Eons Foooo FEFE woos ooono- "flog "3F. memo mFoo_N flood ooooo- mane "an "€55 5 53.8 8.8 F8: 8va oovod moooF "6.85 $85 5&5 "Coke 55.5 "flog "flog 5&5 F 56.25 "E5 R: FFoo_N Roam omFoo 5&5 "ammo 589958.185 "$5.5 Sig £va ":5 53.55 ANNE oi: FK oFoo.N Noooo- "8on9 55mg "AooooF oFom_N 55.8 woo: vmoFo Foifi ooFNN Foooe ooom.o Foam flood foé 53.9 55.8 53.5 x535 Fmooo Boos Noooo- 5K 5&on omomg Footm "Cog 5&5 "$35 Focus oovmg 5 BEN A55 "Sud "8.5 Ezmooom 5 5335 Noooo- Nmzmooom omooom FFoooN Nmoomooom moFoo 58.8 ovmnm 55.35 "flog "Amos "ANFoV "Cos 5:35 omo: Focus 58.5 5va "635 55m. Foam mom; Noood Novoo 5:55 5&8 Nmomg "825 otfi "635 good oovoo $9: mom? Nmoo 83% oomog Nomoe Rooo 58.8 "no.5 Fommo SEN «wood 5 5&5 5;. "393 5&5 "C935 "so. 55".on 85% $35 Nooo.m Nmzmooom "$58 32% £2353. 52.8 good fine Ezmooom :88:25 wood 5&5 5 "A5". 5&5 "Amoov 655 5 55.5 N33 "Amoé "A85 83 mooE 5&5 "3&5 553me Ammov :oFoaoEEm oooqo woo: oooFK Sam ooFod omowm FFoooo "$3888on 856 «mg 5K5 "835 Fmov ":55 #35 5665 flows 28o ":58 5:888on omvoo £8588on FEE woman omooe oFmFF ooooo- $on ":35 ooFm_N "as Bows NEQN oooim oovFF "ammo 5&5 5535 "695 5‘33 Hawks "655 "cog NooE mommg oo.v 9:3 5R. 5535 "Ammo F83 Hams 5&5 "3N9 58.9 "6o. coFoEoEoom "C35 ,Aom2:-_év mmomo FNoE 55.on "$5.5 Foam 5 5 553mb 535 EV Soho Roi 5qu «23 Roim mood nAqua/Howvav Noooo F32 5&5 58on "$5 "Cmomv 535 "ADVISE—555v flood So: omFoK "$.on oomoo voFoK oovos to: F33 Noooo- 55.9 "6.8 Emmg 85d "5.5 5555 "fine N83 5&5 "6on 6.5 mFom_N "Cooo5 55.5 "flog oooms %on So? $55" woFQN ommo.m "$5.5 "ammo "fie Rowm nAOmofiF.—wav "cog 5&8 $an "Amoov "Aooov Nemzn-_§v "Co. "25:8 oFomo $25 55.on 5&5 "float 5528 «NF; So: own: 35d SEN 5528 NoFoo mommg 58.5 £25 5&va 5535 ":35 5 "635 58.5 omooo £3 mom? woo; 55o» 53$ to? 58.25 "F528 good FEE an? "25:8 moo: 55:8 wood "6N5 5535 $3 SEN QBN "6N6 5535 woo: I8;: 5556.8 "635 "awe "of: moomp 885 ovooe 5&3 RN? "C. 55o» 5655 NNFm.N 5&5 56.5 5&9 "835 "6N5 "of: 5 nSo: 5&5 mane flood F82 "flog ":35 F83 535 omono moons mmmFK oooo.m ooFZ "3.85 moNF_N Rood 38g 535 "Ammo "Coo 553 553% oooo em: 885 FoodMane58.15.5386"$588+"53.5%:"AmosNFFoe5:65ooooé"6358;"camoimFéxooNo 5558 FomFF Emoo Fooog Fooog FoF noi: .oz .oz .oz 5: VVVV .oz .oz Fe 8; .oz #35 886"vaN8;"8.9#3138583"8353";59523.""635mg:"8&588g"650me 8N3 wmvma "A 82p "60.5 €de Hats :5 £8; Egg EON." 8; "639 ":35 "A8 "Cod "€35 8." Em? 8:; 58+ mane "C35 "6505 8? ":35 83 8:; mmg "6. "$.05 mnm "$35 $3.? gong Mans $65 name woo: mats 30; 58; mmkp "655 mnomd an.
"C25 ES; $3 "$85 "Amos "awe r "axe 5 mwow ":98 "$.05 "$98 2mg ":35 385 mg} SN; Nooqo- "$.05 Shaw 2N3 356 "8:5 NNEEN "6&5 $va "A39 "855 "3de 38d "8355 "€de "awe 88K £38 "$65 83d 39% Em: "60.5 Noam momma Sod ":58 $va x58 "695 $2.12ka "A535 "$95 83 50.85 "$.05 "60.9 85% name "$35 wmmmd 88.x 08$ 2m; 886 Maw? x35 #83 &8 63 x8.m:mt.:©w_mv "395 K? NE: #98 "demv "835 8mm: "a:5 3 ans mowed among S S86 $2; "E35 ":85 mood vmmvd #95 83K wooed- émg "695 #35 "$905 "So. Hands 85K x35 385 "835 5 A55 Nmzmmdmm 355 2:3 {mam $56 "80.8 83 "835 88+ 2th Em: "625 "and x35 Egmagm "$.05 "80.5 "ate good ":35 ":38 83 "5.5 82% 2:3 2%; "635 235 £9? ":35 $86 NNE "6N5 mmomd $5; Execssam "no.5 "6:5 "@905 "$588:on "635 "$95 "8&5 Emma :53 "80.33me"8535885655 "8:8 38K "$.85 "$5 256 983 «$3 N23 65 $86 88; ":58 "635 $86 Eomd N8: ,Aomzn-_wav "6de 55.5 $5 xmodmvmmmqmxm¢_mv5§mv.m"60.8589183553"$35«Nam"E5BNQN"6:58deéé nACE/51¢? "$.05 mg? "6th "ans Exfi ":0" mag F "A385 Mans commd 98p «on: 6de flood "658 $8.? 3N3 x85 "£35 923 2 552cm 5528 EN 33; x88 "8% ":35 35.13.95 5 8mm; ":25 "$ka "$35 "C35 4?: ,EA: :NE 8me 8va name "6on .2 Efid :33 N83 vwmnm "£58 52 wwwod "Eye mm?5? $th WO 64460 .3 NH 3&0 NH 3&0 NH :8 530 NH NH .30 NH NHxHo NH 2% m m m H am HN- mN 6 - - 5 HH Ho - N - - N N N mm HH HH HH HH HH HH HH H HH m HH HH HH HH m E HH HH HH HH HH HH HH E HH m HH HH HH HH m R m m m m m m m 2358 (Ho Q HN H-m a VS HN H-m a "E HN a E "E HN H-m "E VS oH>H-N Ho-m OSHN 6a HN a «ENE $539800 .2 H N m H" m o N .0 .0 .0 .0 .0 .0 .0 H H H H H H H WO 64460 .3 fizz ME g? mm $7 Ma g? ME mS/ ME $7 «W/ awn/Hz Ma 37 ME HQ? mm g? ME $7 mm $7 wnH $7 3 mS/ mm $7 an: m E": 0 o 0 HH 229m 020% o am HON 6 H m m - 6v- 6% 6-? m S; -- I I Hm- - m; 20 I m EON m I I m mm m m HH HH m HH HH HH m HH HH m HH HH m HH H m m m m m m HH m m m m m m m m m mm HH HH HH HH HH HH HH HH HH HH HH HH HH HH HH AHHHOV am m m m m m HH m m m m m m m m m wH HH m m m : m m m m m m : m m : m ax E w; w; "E Ho-m 6a 6a 6% 6a 6a 6a 6a 6a 6% 6a 6a Ho-m 6a 6% 6% 6% 6% Ho-m Ca 6% 6% 6% How Ho-m Ho-m 6a 6% .oz NMZH a 2 HH NH 2 0H S M: 2 ON Hm NN mm H IO .0 .0 .0 I0 .0 .0 .0 I0 I0 I0 IO H H H H E¢H mHéH H H H H H H H H 2012/071385 .3 2mm/ MW/ 2%" awn/W MW/ 2w." mm," me/ awn/W amm/ 23/ awn/W MW/ 2w." mm," 2W" awn/W am mm MN WW 22-m 6-N 2%.." 20% Mme-m WM MN -o-Nmooim pm; WW 3 N07$ "E Hm; m2 m m I m m m m m 2 m : 2 I m m m m ‘2 m m m m m m m m m m m m m m m m m «2 m m m m m m m m m m m m m m m m m N2 m m m m m m m m m m m m m m m m m #2 m 2 2 2 2 m 2 2 2 2 2 2 2 m 2 m 2 :2 #w-m WM WM WM Wm WM WM WM WWW WWW WWW WM WM WM Wm w-m WM .oz 3.2 8.2 8.2 R2 wN-2 3.2 8.2 :2 NW2 mm-2 $2 3.2 2.2 3.2 wm-2 32 8.2 2012/071385 .3 me/ MW/ 2W" 2mm/ mm." AMA/Hz MW/ www/ www/ MW/ MW/ awn/W 2%" 2mm/ MW/ 2M," ME :2 WMWHM WW 76% 020.2" 57:" as? 220-? 20-? mm 3 020-? WM E 5-3 MMWHM 20¢ -ofiooim m2 m I m m m m m m m m m 2 m m m : m ‘2 m m m m m m m m m m m m m m m m m R m m m m m m m m m m m m m m m m m E m m m m m m m m m m m m m m m m m #2 2 2 2 2 2 m 2 2 2 m m m m m m m m :2 WM Wm WM 6a 6a 6% WM WM Wm 2>o-~ 2>o-m 2>o-~ 2>o-~ 2>o-~ 2>o-~ 2>o-~ 2>o-m .oz :2 $2 $2 3-2 3-2 3-2 $2 $2 32 8-2 :2 NW2 $2 E2 WW2 82 $2 WO 64460 .t awn/Hz awn/Hz am," "NW/W mm $7 3 g? Ma $7 "NW/Hz awn/Hz Ma mS/ me/ 3 mS/ awn/W amm/ "NW/Hz ME $7 2 am m; oEoN an: £3 mN 3 "E a WN 6% Ea Hm: mN E 76% 6N "IV 76-? N07$ i Wm 3 6N mm m : m E : m m : : : m : m m m : : H m m m m m m m m m m m m m m m m m R m m m m m m m m m m m m m m m m m an m m m m m m m m m m m m m m m m m R m m m m m m m m m m m m m m m m m D D O O D 0 Q oSoN 2>oN 2>oN oSoN So So So So So So I I I I I - N N N 2>oN oSoN N 2>oN N 2>oN QSON 2>oN N oSoN .2 NW2 $2 8-2 3-2 No Q E $ as p I0 IO I0 8-2 I0 .0 I0 H H 2-2 :2 NEH H H 3-2 M32 H H E2 WO 64460 .3 MHZ MHZ MHZ mm amm/ awn/Hz MW/ mww/ MW/ "MW/W «W/ MW/ amm/ MW/ MW/ mww/ MW/ am 6-m an: WWW" m "IV 5N MUM 6-? 22+ E 5m: "3 mam min 0323 £04" am mm : m m m I m m m m m m m : I m I I H m m m m m m m m m m m m m m m m m R m m m m m m m m m m m m m m m m m R m m m m m m m m m m m m m m m m m R m m m m m m m E m m m m m m 3 m m Q EQN 0:23 220-~ 2>-~ 32 2>& $2 SE 32 32 0S-N 2>-~ 32 2>& £2 32 32 52 m; £2 RE w; 9-2 8-2 $2 a: $2 $2 3-2 $2 $2 $2 0: 8-2 3-2 WO 64460 .3 awn/W MW/ 2M," awn/W mm." 2W/ 2W." "WW mww/ $7 2%" "WWW 2mm/ 2mm/ "WW 2W/ ME am MN 222 WW WM WM 224" 222 MN 2mm -ofiooim 220+ N9: 2>E 6% 2 22 2": m2 m m I 2 2 m m m m m : 2 : m m m m ‘2 m m m m m m m m m m m m m m m m m R m m m m m m m m m m m m m m m m m E m m m m m m m m m m m m m m m m m #2 m m m m m m m m m m m m m m m 2 2 :2 2>§ 2>E 2>E 2>E 220-~ 2202 220& 2223 220-~ 2>E 2>E 3: 2>E 2202 2>5-N 6a SN .oz 8.2 Q2 g2 32 00-2 3-2 M32 32 £22 2% $22 £22 £22 2% £22 $22 -2 we WO 64460 mane Boa: :9: $33 5&3 5:9 mama £25 Amwe 5:: five man: mews 3&me mews :30 :3: gm: so? p.02 033 Pom: #3: am? $$N 9&2 SN: m2: mg? :33 3.: éwa 803 Ea: Rm: 33.0 :2: mam: £98 A38 ASS :3: :33 "have magi AS: AS: :38 0:2 38.0- gas £33 memdogoa :33 :88 3:: Swim $8.138253598 Emg mom: so: 0mm? 38m ONE: 2%.» 9:3 ASS $3: :35 .3 :27: 5N8 9:2 E: @093 wand $53 A38 m5: Xmas €me Amms wmmmiamfiv 3:3 525 macs Amos 5on 38.0. mag :88 ANS: 60.0 mama 30: $82 :0: o8: 33 can: 93$ 3m: N83 :38 :53 2&3 : 3:: 0mm: Amos $53 Ammi mew: mew: 5%.: m A3: 53.: A31: a: no 38.0 N om: A38 5:: :33 Pow: N83 $53 $3.138: 0E: OS: 53 5R; 50.3: :3: 3w: 32% £913833.138 ASN.3 32 9&2 NE: 33.: 51:: m9:: m60.3 :33 mam: gas gums :82 ANS A33 :3: m8? mam: E3 m: m :98 2%.» :3: Amos 5&9 £5 Sow.» 83.0- Emma :32 am? $02 $03 23m :3.th $8.0- :3: 0%: momma #58 mews £va $03 9&2 E: saw: WES: Maw: 8328me five 5%.: £on 5on £02 :33 A59 :2: "awe SS: v: E 38856: 3 538 momma Es 5%.: Ag: 2%? 83.198 mama: :68 :53 6qu 83; £35 5: 3%: $03 :35 88.0- 89: 28.5 Emma Amos $8.0- Room Amos Ho: WE); NE: #22 88.: flow: A38 £3 88.0- :38 £58 5m: :38 32 mElv 5&5 AR: :25 $53 M: sougswmqg £23an 983 mew: :58 A03; Amos 53?: Ezmaém 83.» :33 NR; :83: 3&2 568 New? 9:2 3:: Sam gas 38.0 Bows 3%: as? mews £8m :03: $53 go? 83: 3:: 88.0- :03: 5.8 Acaméwmam $03 NR? E2253 :03: :38 55.3 52:3 032 :38 E2353 £2 mews; A03: m3»: A2,: NEE N: 828% 3:.» 5%: 5:3: A8: mad: 53; Saw 3%.» "Aware :33 3:3 32 E: mmgm wave ONE: 033 3%.» 3me :2: 28.me RBEOU‘EEO Ezefitam "Ex: Sam :3: mmmm: 38.0 ussagim m5.8 x8: Ammiommwm 3.3 $3.: 5:82:35 :38 Wave m2 m5.8 52 :3: "hazaohooam"A8293? Ewe A2,: x30 32a 29% :3 39% mg: 23.: 6.0 553 :69 ME; 8%.» $53 A03; EVEN 3N2 N3: m3: Amos 8mm: 35; 085 :83 :33 R : 059 £3 m aAcmzn._§v 53; 88a "9&5 M33: 8mm: 83.0 Nemzn-_év ma: WE»: :53 Nazavav :oEOmefiwbm £2 No3: A6,: A39 mews mews mate A6: A6,: 5%.: meta :a "25:8 Snow mews 39$ $0.: A38 A2: 9:; :8.» E; :38 ASS 83w Mam: Mail 33 $8.158 £2 to; RN: 9E: :33 Q E Wm ma 3 5&3 Q: 55:8 "25:8 :.m x380 :8: :32 Ego E; am & mane éw: Amwwws 033 $3.: ,3 5&3 Amos :53 :38 :38 Age WE»: :84; 8310ng : -2 -3 -2 52 -0: 9: BEOmeB: .2 0&3 N22fivcgmamA3532:£9832:£0.85;fiwdgocmmfiawe$313.88mgmew:33.1%.:83:3808: :35 :83 mews :38 5:.3 .oz EV; 0:: 33 :38 :28 .oz Show mugs So: mg} E3138 0%? 3528,2257: Moog N8: 03: @983 Room 38.8 88.0- 88? Now: 338 38.8 38.8 33.: m£38 388 New: 83m 33.8 8mm: mg? 8%.» 338 33m 3%.: 338 338 32.8 32.38 swam 333 852 NS: 33m $33 $83 £sz 388 Kama 338 30m: 38.8 53 8:; Em? 38.0 3380838338 33.88 38.8 m2: men: 38.: 3.8.8 338 32.8 3%.: 388 38.8 88: ammom 38.88 39.8 Emma 388 Em: 33:8 who? 88.0. 33.8 38.8 3R8 33.8 332: $83 £33 8%.» 882 :83 8833 380.8 33.8 333 38.8 383 3288:3133 Show 33.8 $83 33.8 88.0. $me 833 33.98 38.8 3%.8 Emma 388 WE: 33.1383st 3388 338 ME: 5: R5}38.830338.83188 338 3868 388 33.88 332 88.0- 3888 E: 8qu 33.38 388 38.8 832 88.0- 333.8 33.8 38.: 883 $8333.883188 3%: 328 $83 28% N3: 883 388 we"? 33.: $83 38.8 32 338 38.8 38.8 #22 88.0- $83 88% 33.8 388 as; mama 33.8 38.88 35.8 33.8 3%.8 N83 33.8 :33 a»: 38.8 3&8 3828 ENE $83 3E8 mow: .283 33.8 33.338; 388 RN? 338 38.0 33238 38.8 38.8 3E8 :83 :82 88.0- whom.» 8w: new? 33.8 E83 38.8 33 E83 38.08 New; 33.08 momma ME} 3%.: 88; 332 323 3:18 £33 38.8 3.: 882 33.8 33.8 38.0 33.8 32.8 33.28 3&8 32.: 883 388 8%: 3808 29% ma: 8%? 0%: 3%.: 38.8 338 $83 33.8 38.8 3838 882 383 38.88 $3.3 3338 882 38.3 cm»: 338 88; momma 338 38.8 Room 33.8 Room 338 88; 38.38 333 33.08 332 88% 3%: 338% 3:8 33.08 33.8 39; Room 39% 38.8 082 33.8 38.8 38.8 3E8 $2 38.8 088m 388 033 an: 38.8 88; 3 33.8 33.8 383 $2; 38.8 38.88:.m 833 33.8 3%.8 33.338 33 355 E83 mowms 083 338 :82 EV? 338 883 338 3R8 33.8 08$ £38 38.8 3%.8 383 52 M35 Ema 32.8 082 288m 38.8 3on8 3%.: 38:38 39% 3:8 38.8 38.: 32.8 $33 383 38.8 332333 m8? 333 33.8 332333 833 33.: 98% :83 $83 823 88; 3:8 33.8 38.8 33: 338 $5 Roma 83.3 woo: 332 383 33.8 338 8%: 328 883 38.38 882 38.38 883 3888 3322.33 38.38 $8.5 :33 3&8 332?de 33.: 38.38 83m 38.28 : 8st Ezmagm 3828 3803: Room338833.138 38.8 3322.33 388 38.: 33.8 883 332333 882 33.: amNOV357 E; $83 38.8 Ezeggam"AOmEQ-vav $83 33.8 083 "Evachoam 380.8 $83 £82 usuaitam 3%.8 982 3&3 38.8 838 33.8 38.8 833 33.88 38mm $8.3 95% 3%.» 95.3 33.8 $83 388 3a.: 8833 3&8 mg; 38.88 :85 cam 38.3 $23 38.38 338 3888 33.8 5.2 3%.» 3:13: 32.8 EsaitoamNOV357 38.8 £2 38.8 savage-am 33.8 3a.: 38.8 383 33.8 EN; 53 3%.: 38% 23; 3388 833 .AOmSQ-vav -vav 388 $88 38.8 3E8 $33 3&3 3%.: 3&8 082 88.0- 838 38% 338532 33.8 momma 28% :82 883 38.8 83.5 3%.: 328 $33 3828 38.8 823 3838 $38 3&8 sacs 883 33.8 3E8 8&2 mom: 3838 3838 38.38 3:: 883 33.38 .AOmEQ-vav 338 38.8 38.8 833 388818.88 "huseohooamNon/323-357 38.8 :8"; am: 38.8 88$ 33% 338: 3 30338 353cm 353cm 38.8 8 EN 3538 838 385 33.8 N82 "253cm 303 3E8 33.8 33:08 32 88.0- "3538 3:53 mm? 38.8 823 353cm mmomw ca: 3833 38.8 88A ".538 3: "2 388 338 $3 33.8: ,2 338 823 338 88.0- .2 38.8 83: $3 38.8 $33 ,3 3%.: Mam: mam: 383 388 3%.8 a: 38.: 38.8 033 32.8 ,2 38.38 38.8 38.8 OR; 333: 3: 38.8 -3 -3 -3 -3 -3 -3 -3 .24 SW; 98%.» 3888 082 52 Saw 33.8 ENS 33:8 .2 :83 33.8 3S8 333 33.88 .oz 88¢ 38.: 38.8 38.8 E2 88.0 .2 N33 Rm? 338 mm? .2 Exam E: $3 38.8 082 .2 33 323 503V gas meme Age 5:8 maps 38.0 338 five - wave 338 fine $on 88.0- 553V 383 :02 03: £03 9&3 Rm: mm?» Emma its$8.138ESNMSEV$313.: 5on 3%: 03; 0?? mmwdm 32.me $2: :53 2%? $me 2%? mac: ASE: WE: maveomimabe SE3 fine 5on $on 033 38.3 mete mews $8.3 £58 383V 5:: "3.33 083 mat: 3:: S3138 E: 083 2km 80: 2313.8$3135003aAXW.EWS.m 338 $83 N3; swam Mao? :93 WSW.» 83m A303 $90.» Ema £83 $33 flaws mate 62.3 as: $3.3 2%.: $0.8 RES 5N3 m8on mama 38.0: 8me mam: €me WEE Amwe 832 $0.8 &3 32.: 50.8 Amos $03 033 $8.0- am? 38m $8.138 $8.3 9%? 2%; Amos 83.5 33.8 253 Sm: $83 55: :05 :03 mm: "ES $3.138 £33 A38 mam: mags Ami-V $0.: AWN: 3%.: mend mom? fins AB: 38.3 mam: £2 :: 0%? 5%.: mac: £3: 863 33 2 88.0- $3 0:3 3: MRS N32 .253 mam;55.8302A8389;52:me£3.3Vmomm.m mane 88.» $3.0 932 mNNm.m Amwe meme $8.5 com: SSN m5»: £58 WARS 32$ £9233ROSES; AteN3350.:022Amwovommm.~m§§s m5»: 53.8 "so: £2 s WES 3%.: 32d 5on ASS EVE Age Ass 533 32a $3 88.0 32; 333 38.» $318.5 $35 $on 88.» 2%.» 0%? 383 233 835 doavfimam Ewe 3330mm? $2: 53.: momma 38.: £8 ANN: Age 509 AWN: mew: £3.16.me 39$ MSN: 33mAwmdoswmvmafiwe 50.9 £83 memos i3 $on ASS 883 38w NE: ~33 28s Ewes "sums 3:: as: m9? sum? 568 Sums 333 :35 :8 38.3 ARE: A86 33.8 mag: Amie Rowe mam: Sag 333 m:98 38.: 55: §3 553V A3: 5-3; 082 53 333 amnm 883 083 83a Maia 3322.33 Sm? 33: 3st :83 N93 88.» an? 38.9: 5&2 we»? Acme 5&8 303 022 358 38.: 332333 €35 35.: Ezmagm 33.1%.me mamavmmwdm 53: 32.: 3322.33 Nae/32.3% 352.3% 33.: msmd 3%.: 083 mama: £3; $53 ins mews its :BoagooamNemznéav mpg: $03 302 RN? Emma "Emachomam «a; E: 33.1033":$8.163: Exachzam Ex? $8.» £83528 am £an we: v8? mafia :BQEEUEm E53 :03 33.: mews; "$388303 $03 mo: $3 ems A33 39% :5 38.5 6on mam: Ammow: so: £on €on x38 m80.8 mawe 53$ N82 5&8 #3; 82a 38.: mama 333$ 88.0- 333 €on 9&3 $va 33.3 NOV37 9K; 8m: Emma $8.0- nAOmSE-Edv momflw 8%: wwwma533333-893 m8? as»: nAcmzn-EV N83 mg; 52 513.8 .AOmzm-vav waflw 53 émi Nemzn-vav M33 a?» 8va fine 568 88.0- mama Amwe $33 33.: mg: wm 32.3 AS: Raw: 5&5 $8.0- Amwe 38.8 ANZV 5"? mam: A2»: $03 33% 5%.: gas RR: $2.3 EN? 5&8 3538 38w $3 32.3 "3538 mew; 3m: 88.0- £538 033 333 3 32 33.8 553% $33 KN: $03 mews £538 28w 0:3 $0.: $33 ".538 Emfiw E: Rama £58 333 :23 ,3 ice Age 083 new Age 3%.: mama $02 As»: 3" 32.8 AS: 3%.: 88.0- a" mag: m5»: 33.8 963 32.: a" Rowe 38.3 Niam 53.8: i Ate 38.3 wave :32 83m 33.8 -352 33w 8m; £30 -3.24 033 mm: 3me 38.3 98.0 -3 -3 -3 52 83w ME? 803 Emma :2: -3 53.8 .2 $53 m3: 23a 88.0 .oz Smow $3? 38S 382 :N: .oz wmmcw $2 am? 38.8$9.188womgéoe333%me$913030:£3.13.ch083AwoxocfionméiaEENAEQ wane £5: - 55353 £5: £5: 5%.: £5: £5: £5: £5: 555: 55.: £5: £5: 55? 5:55 £5: £5: 5%.» $55M 5%.:55.1553525n: 53 5:5 £5,353,155: 5:: 855m 55.5: 5%: 55.5 »:%.N £33 £55 SN? 53: £53 £5: 55.: 522 5:53 £5: £5: 55.: £5: £5: £5: £5: 582 55: £5: 55: £5: £5: £5: £5: £5: £55155: 58: £53 £5:5&353:55.13: 55555 55: 5555 E5.» E55 £5:; $55 £5me mom: £5? ENE 525.5 OE£ 55.: 555m :5: 5»; £5: £5: 5mm? £5: £5: £5: £5: £55: 555.1555: 55.: 55.5%: £5: 55: £5: 55.: 55.: £5: 55: 55.: 55.: : %.» 255m £5: 25.» :53 5555 £55» £55» 5: 5555 5%.» 5:5 £58: :53 5525 5555 952 55% 55: £5: £55 555.5- 58.3 £5: £5: £5: £5: 582535: 5- £5: £5: £5: 55.: $5.15.: 55.: £55: £5: £5: ONEN 255M£N:ES£ £55: £5: he": M555 £5: M55.» :55.» 5555 £52 555.5 5:5; 555.5 55: 5m: 55» : £55 5: £3: $555 £5: £5: 55E £5: 5: N82 55.: £5: £5: £5: £5: 3:2 £5: £5: 55: 55.: 35515.5: 252 :55: 55.: £5: :52 55%5 £5: 55: 2:: 8.8.5 £55m :33 £5? 55.: 55%: £55 £85m£5::5:255:25255.: £5: mg? £59: £55355 £55: 585 255 £55: £5: £5: 5mg £5: £5: £5: £5: £53 55: £5: £55: £5: 55.: 35.15.: N2253:55.12»: £5: 552 £5: £5: a»: 555m 5%.» $3.5 5%.» £55 £5: a»: 555.5- 25%.» 55:» 5:55 %.: 52%5 3%? 5:5: 5:55 :55 58255:: £5: 55.: £5: £5: £5: £5: :53 555-55:58:55.5: £5: 55: £5: 55.: £5: £5: £5: 552 £5: £5: $25.53 £2 553.5 SEN£%.:$»££5: $55,155:: £25.35 55.» 25.» £5:§%.m55.:5555555352 385m£%£w:»5%££%: £55535 NR? £55 £5: 2:: 555.5 $5.155:555555.: £55 555%.» 3sz 5555 £35 £5:$55m£m.o:$om.m £55: 5555 555m £5: £5: :25 £55: £5: 55.15: 55: £5: E3 :525555:5253:5525555: $22.53 £55: 5:: $25.35 851%.: £5: £55: £5: £5: 5353185: $25.35 £55: £55: 522 £22.35 £55: 55: osm££m.:5~m.~ 55585855 $6.5 355m £5: £53 55.» :53 :53 £5: 5355 3555 553 55? NEE 85.; 55: :55 555.3 £5: 55.: 35515.»: 5555555: 5582535 £3 £5: 95$ 55: £5: £5: 2322535 £5:155555:55.25: £5: 55: 55885235 £55 £35 5588525 53:55.: £5: 55.1%.: £5: £5: 23285555 £5: £2 5588555 £5: £5: n$555.37 59%5 E55 mwfi££5:: £5: nAOmSE-vav 55555 $5.5 5%.: 555.5- .AOmzm-EV 5:; 955» .3525-va 26.5 :53 £59325 552 585 555» 5555:5555 £55: 55555 £5: £55 235 55.155: £5: 55.: 9555 855- £5: £5: 553 555: 55: £5: £55 £5: £5: 5%.: N05255:? £5: 55.: £5: 552 .AOmzn-vav £5: 52 n$525-va £5: 55.: £55 5555 555» £5: £538 382 £5: "55355 55555 £5.» 55.: 5555- 552.5 8:; $53 £5: 5:538 :55 5%.» 552 3528 :85 N23 £52 555: :355 55555 £5: £538 N255 £555 £5: "mm £55: 55.: N85155:: £55: 3553 5 55: £5: 5555 55.: .5 £5:: £5: 55555 nwa £5: £5: £5:5E5m £55: a" 55.: 55: £5: EOE 45 £5: 5:55£5:855m55:55.13: :53 E: a: £5: 55.: -3 £555 $5.» 582 £5: -3 3555 5E5» 5%: £5: 555.5 -3 £3 N33 55: M553 -3 E55 :5: £5: 39% -3 $55 :5: 555m £3: -3 -3 .52 .oz .52 .2 .52 .2 $355 £53 £5: 85.5 .52 5555 9%.» £315.: 38.9 33.8 Ema N33 33.8 88.0- 38.8 33.8 33.: 38.9 3&3 339 33.8 388 RN: 33.0 $33 38.2 $8.0- 3890:9188 $83 38.0- 032 $83 3N9: 9 38.39 am? 33.3 $3 33.9 33.9 90me $2.3 men; 9&2 389 33.9 3S9 333 33.8 083 38.9 38.5 398 33.9 33.9 38.0 33.8 398 3399 032 @983 389 338 33.8 033 88.0- 3338 $9; Sim :53 32.8 32 :3.» 38.39 38.8 Ema38.98333%.9353338 W993 9%? 88.0- $8.3 3m: SN? 338 398 $me :33 $33 32.9 38.8 38.9 833 38.09 33.8 38.38 Room 38.9 3%.: 33:8 38.8 38.9 3338 3&9 383 88.3 33.9 Ema 338 33.: 3336 88% 333 5%: 338 $33 339m 3%.me 38.0 $33 9&2 38.0 23.3 8&3 $33 3&8 3%.8 3w? 38.8 8va 88.3 339 :33 3%.: $33 M: 33.8 33.8 N33 32.9 $8; 32.08 9 33.8 33.: 32 32.9 33.9 338 329 322 33.9 33.: Some NE; 3%.: mag 52.3 SSN 33:8 wow: 83.3 383 32.8 :33 383 as? $33 388 3&8 833 mg; 39089 3&3: 932 33.9 932 33.8 N83 38.8 32.8 38.8 #83 33.9 38.8 933 33.38 338 38.8 33.9 $33 032 33.8 392 339 33.39 20.3 333 389m 3338 $8: 33.8 3%.» 333 3388 398 $3.3 $sz389N93333.838:388%38 Sm; 3339 $3.3 $33 933 833 338 3%.8 $33 $ng 3933 3528 398 3%.: M302 339 $2 38.8 33.9 393 38.8 38.8 082 33.9 3R8 38.9 3898 E2 33.8 3S9 33.8 mg? @303 3938 won: 3&8 333 083 0:3 832 30.0.8 53 £33 3888 $8.3 033 333 33m 3098 333330.09 333 :03 802 339 33.8 38.9 MS? 3%.: 332 39839 38.9 33.8 Roam 33.8 3328 302 3:8 38.8 33.9 3&8 $33 38% 38.38 38.9 3%.: ~33 $2233 WEE EN? 3339 Nmzmagm 353 3:38 382 3322.33 $2.» E? 33.8 $2 $33 33.39 E? 39; $3 Each 328 333 303 Emma 3%.: 38.39 389 2 38.38 momma 33.08 3R8 38.8 333 3E8 3323.33 38.9 3 33.9 3323.?»- 32.9 33.: 33 $23 3838 322.3% 3E8 33 32 32 3.9 3.9 3399 332 33.9 "Eveofioam 893 Emma 38.9 32.: 082 :9; 983 38.8 933 33.8 $2.3 803 233 9393 38.9 353 953 $33 398 88.0- 33.8 338 339 EN? "Emachomam 303 38.8 932 33.8 "hmaaechooam 3%: 38.38 033 $9138 "$382383; 38.8 £2 33.8 :Baaohooam 3%.8 38.9 33.8 :33 :Baagoam 33.8 338 32.9 E3 398 88.0- Nazi-av Show 9%? 3:8 -357 3%; 33.9 N83 NOV357 $38 $8.8 33.9 932 NOV357 wow; 338 33.3 NOV357 333 833 $3.» 3E9 $99 :33 $33 $3 338 28.3 33.8 339 38.9 383 699 3E: 3?? 3%.8 3E8 3338 imam 3:98 38.38328 3%.88 $va 339 38.38 38.9 3R8 $33 88.0- nAcmzn-Env 3%.: 33.8 38.9 $3 3%.8 022 "253cm $03 953 388 88.0- "2538 $03 33.9 Room 38.9 353cm 833 $3.0 32.8 98$ 3538 N32 33.9 SR3 3983 3E 33.9 3538 53 3E8 35:8 ~33 233 8an 398 $2 3K8 ,2 38.8 38.9 33 3:8 "mm 38.8 Room 33.8 $8.0- 3% 38.38 3:9 3933 38.09 ,mm 38.8 38.: 333 33.8 am 32.8 38.8 33.9 mm; $08333331823388$023358 ENS ,2 3E8 38.8 33.8 $33 33.8 comma -3 as; as: 333 -3 033 33.: 3339 -3 .oz 3:8 .24 Ema 52 $33 :33 33.9 $33 39»: -352 033 0mm? 38.8 mama 38.: -3.2 Raw is.» $3.» 38.39 832 32.9 -3.oz wag 88.3 9393 38.9 :32 38.8 33.8 33.: 3&8 3mm: 33.8 33.8 $8.0- 38.8 3mm8 302.8 380.0. 3%.8 883 gm? 0R2 8&2 $82 .982 232 3338 :2: 5V2 0:2 88.0. 862 $2 3228 £32 :32 333.08 3828 :02 2&3 8&2 882 3828 3%.: 3338 3:38 38.8 388 38.88 882 3828 33.8 3228 38.8 302.8 338 332 33.8 328 3828 3388 33.8 33.8 38.8 852 E33 £22 88.0- 8&2 332 M82 $2 38.88 32: 282 $22 38.0 332 mama 332.8 E382 832 $22 88.0- $82 83: $32 38.38 33.8 3818 328 38.8 38.88 33.8 3238 338 232 3E8 38.8 32.8 33.8 3:8 338 322 38.8 88.0 38.8 388 35.8 3%.8 338 38.8 302 33 882 23m 52 $2.3 :32 38.8 E2 832 $92 0:2 3882 382 3028 33.8 302 3E2 382 522 flood 338 8382 NS; :83 302.08 338.8 32.8 32.8 38.3%: 3:: 338 3238 22 88.0- 38.8 3&8 33.8 3%.8 3:8 332.8 2232 38.8 3S8 388 338 33.8 33.8 332.8 882 823 833 Mac? m2: 83: $2 323.8 :22 852 882 $22 0&2 332 328 E23 322 52 2.82.3 E; 332 38.238 $2 33.8 22: 33.3 38.38 338 338 338 33.8 3828 :32 33.8 38.8 33.8 33.8 3%.: 38.8 $82 38.8 33 3:28 38.8 338 388 $2.3 222 32.: 38.28 232 3.8 $22 833 $2 38208 282 282 E2 38.8 332 382 282 322 mg: 382 38.8 382 223 882 $22 an; 388 $83 32 33.8 88.0- 3%.: 382.8 32.8 382 3x8 3&8 33 33.8 3.8 882 38.38 33.8 38.8 38.8 332.8 33.8 $2 38.38 33.8 328 33.8 32.8 E22 @022 32.8 338 M22 3E8 22me am; 2232 3058 0&2 3882 $2 388 52 $8.» 882 8A2 who: 282 328 282 cm: :22 M322 2%; 33; §2 3%.8 223 388 388 3828 388 322.8 2232 38.8 38.8 388 E2 398 3%.: 3a.: 33.3 328.8 38.38 E2 3R8 38.8 38.8 38.8 33.8 $22 3M2 38.8 32.8 @282 382.8 332333 E3 333w swam 38.8 $28 332333 323 3 822 $03 388 3322.33 $2 @532 3322.33 332 3%.8 @883 $82 32 33.: 3338 m 822 @223 883 8&2 3322.33 $32 :33 882 3%.8 8.83 38.38 338 33.8 322 88.8 38.38 32.8 3&8 88.2 8A2 3%.8 38.8 33.8 3388 32.8 3838 $32 33.8 33.8 3&8 :82 3358 38.38 32.: 33.8 862 338 "Emachomam 8&2 ME; $02 38.8 38.8 032 222 882 33.8 832 2&2 #32 822 802 38.8 832 3m28 £82 :82 8E £82 82 8:3 $2 33.8 $22 33.8 33.8 38.8 83.2 $23 LBQEoEEm 3R8 382.8 388 52 Esaguam 3&8 323.8 38.8 "ageofioam 0232 33%: 3288 3:8 3028 38.8 328 33.38 "huauachoam 38828 338 38.8 38.8 8&2 3R8 NOV357 8&2 882 mm; 332 38.8 388 nAOmEn-Env 8%; 382 «$2 33.8 .AOmzm-EV ES 8%.» :32 NOSE-EV 8332 :83 38:8 832 "MozachoamNOSE-18v 3&2 $8: 32 NOSE-13V was; $88 302 33.8 :32 3%.: 3028 382 33.8 3%8 :82 $22 33.8 38.8 328 $32 3%.: 33.8 38.28 33:8 853 082 3028 3:38 3mm: 3:8 33.8 3838 38.8 3%.8 352 338 353cm 228.3 wow; 8352 38.8 38.8 as; 882 33.8 £92 38.88 38.: 35.88 353% MS2 39128 353% 88.; So: 23.2 638 3538 832 283.8 382 3538 59% 2%: 822 3538 $83 $3; $02 302.8 $22 nwm 38.8 35.8 3:8 52 332 am 3E8 33.: 3818 52 3:- 3E8 3838 328 882 38.0- 3808 38.8 $22 £- 3838 ,2." 35.8 38.8 328 £02 .8- 3E8 38»: 3%.: 8&2 338.88 -3 -3 -3 -3 -3 -3 .23 88.0 wag 0%? 38.8 38.8 .oz m3; 282 832 35.8 382 .2 383 83: 8022 3828 3228 .oz 352 853 3233: 882 3E8 .2 :33 wow: $2 32:8 $2.8 .2 833 Ewow $32 38.8 #92 582: m:28: $2.: 582: 58.: - 58.8: 222 8222 W222: 88.2 2:82 m92.8: 22.: 5222: 58.: 22.: 22:2 2282 :32 282 322: 22222 .822 822.2 228.2 82: mA2222: $22 8222 822.2 m82.8: 523.: 522: ME: 882 58.: 822: W822: mGE: 582: 58.8: 522: Mai: W63.: 522: At}: mA222: m322.: A222: 22 W282: 228.2 52.3: 322: £82 2822 882- 382 332 228252222: 2282 22222 :82 882 2;: 8:2 22.222 282.2 2822 228.123: W82.: 822 m8.: 222 822 :: 52:: 5222: 22.8 mE2: Ami: 88.13.32: WE»: mG22: A232: 58.: 2222: 522: 5:2: 58.: 582: 2:2 8222 532: $8.2 2282 882 8:2 232: 8222 382 832 58.8 :22 822 82: .8232 52222: 8222 2222.2 8:2 522: 28: :22: 5222: W232: 5:2: m8.: 522.2: 52.22: 2825222532522.: 5222: 52.8 58.8822.122.88225222:2222 W822: W522.: 822 892 2222 22.8 522.: 22: 882 5:}: W322: m8.: 22.8 52.: 82: 228.2 88.8- @222 822 2322 2822 222: 22322 522: 882 822 82: 822 m52.2.8: 22222 282 $32 2822322:882.2§2.5 WS»: 2282 58.: m523.: 5:2: €22: m22.: 5%.: 5:2: 22.8 m2.: 522: 2222 m52: M22: 82: m2.: 522.: 282 58.8: m8.: W322.: E2: 328.2 W222: 882 282 8222 822 28: 2822 222: 8222 52.8: 882 2832 332 $82 m222:2825R2:832.1222: 8222 222 882 2232522.: 58.: m2.: 5822: 382 58.2: 522: 582: 62.: mE»: 2222 2222: mG2: 82 52: mA222: A222: 522.: M322.: 5:: 52.8 822: 882 8222 22222 2822 58.: 882 22222 m82.8 82: E22 282 2282 A2232: 2222 2822 228.2622: 8:; 22222 8222 2222 22222 88.8- 522: mE2: mQ22: $2: 2282 A222: 5:: 52.8 522: m22: 52.8: A28:82225283282 A22: m€22: E2 282 5222: 282 A22: 582: 22.: 52: 58.8 582: 522: 33222.82 23222 88.2 2:22 33222.82 22222 5222: 22222 3328.82 8222 22222 52.: 3328.82 5: 3222 A8,: 3282- 832 2:22 £22: 28: $222 228.8. $82 2222 8322 2222582.888.1228: 232.3 52.: 2222 522.: 5%.: m32.2: 882 W222: 88.222: 52.8 522: $2.: 3282 522.8 W882: 2222 532: 33222.82 W82: 522.: 282 33222.82 W882: 552: mE2: 3328.82 53.: 58.: 518: W322: 332882832 832 882 $222 5222: "$388382 2822 5:2: 882 2822 :22 £22: 88.8- :92 882 5222: 88.8- :22 22222 522: 882 832 228.2588: 882- 882 282 8222 822 A222: M32.: m82.: 282 m22: 282 5 mA222: 32: 2282588: 5:88:82 m5.: M22.: 282 "$882382 53.: 5:: 228.2 5222: 332882832 52.8 522.: 832 .32 mG22: M33.: 882 M5.: 5:88:82 5222: 52:: M22: ME}: -37 3222 8222 8222 mG22: Nemzn-vav 8222 ma2: 2822 "Acmzn-vav 8322 :22 522: 3222.3 NOSE-58v 2822 2822 m322.: E82 2822 $222 m:2: 22222 3222 5222: 2882 8222 282 #82 22225228:88,122.: 52.8: A22: A23: E2 522: 882 A22: 88.18.: mA222: W922: 282 58.2: 522.8 WE»: 2222 mA222: "$223-va mA22: mA222: 2222 22.: Nemzn-Tav RE: A232: 522.8: N02233§v 582: A38: 58.: 82252.: 38392 2282 2222 882 52:: €382 $82 522: 382 2838 32222 382 532: 822 €3.82 2822 88.2 W882: 2222.3 882 A82: 228.8- 8222 :82 88252.: 2222 882 58382 22222 38382 2538 2822 282 88.2 382.18.: :" W82: 5:8: 58.2: 52 ,2." m22.: 522: a." 588 82.: 882 5222: 22 W222: 5%.: 832 52.8 ,2." m$2.8 mE2: 282 522.3: ,2." 52.8: 522.: 2232 52: ,8 WE}: A82: m322.: 2222.182: -3 -3 -3 -3 -3 -3 -3 .24 22 82: 2282 W322.: .2 2282 582: 82222 222253.: .2 382 822 522: 282 52 832 228.2 m62.: 222 .2 2222 8222 522.8: 882 52 8222 82: 522.: 822 .oz 8322 2232 22222 222222.: 282 mA333: m3%.: m333.3: mA333: 3333.3 m333.3: mA333: m333.3: 5333: m:33: m333.3: m3%.3: 53.: W333: m83.3: m333: 3333.3 333 33 3333 m333.33: %333.3 3333.3 3333 3333.3 3333.3 3333.3 3%333 333.: 333 %3333 333%.3 3333.3 833 3333.3 3333.3 3333.3 mA3333: 53.: m3%.: m3333: 3333.3 3333.3 m3333: m33.3: 53.3: 333.3: 3%3%3 3333.3- 53.: m333.: m333.3: m83.3: m333.3: m333.: mA333: m83.: 53.3: M333: m33%.: m333.33: 33333 3333.3 %.3: 3333 33%33 mA3333: m333.33: m33%.3: 33333 3333.3 3%333 33333 333 3333.3 %33.3 3333.3 3333 3333.3 %33%.3 3333 3333.3 3333 3333.3 3333 33%33 m3333: 53.: M33.: m333.3: W333.: 3333 3333.3 3:33 33%.3: m833: m333.3: M33.: M83.: 533: mA333: A333: m33.3: mA333: M33.: m3333: m333.3: m333.: M3%.: m333.3: 3333.3 %.3: %333.3 %333.3 3333.3 3333.3 333 %333 333%.3 5%.: 3333.3 3333 3333.3 5333: 3333.3 3333.3 3333.3 333%.3 A333: 3333 3333.3 3333.3 3333.3 33%.3 3333.3 3333 3: m33%.3: m3%.: m3.: %3333 m83.3: m333.3: 53.3: 333.3: m83.: m33%.: 533%: 3333.3 m83.3: m333.3: m33.3: 5%.3: 3333.3- m3%3: m333.: m33.: m333.3: m33%.: m333.: m33.: 3333 3333.3 333 3333.3 333.: %3333 W333: 3333 %333.3 3333.3 3%3%.3 523: 33333 m33%.3: M33.: 53.: 3333.3 3%333 m33.: 3333.3- 3333 3333.3 3333.3 %3333 3333.3 %333.3 3%333 33.3: m333.33: 3333.3 3333.3 3333.3 A33: m333.3: E33 533: 5%.: m333.3: %3333 3333.3- m3333: A33: m33%.: m333.: m333.3: 333.3: 53.3: 53.3: mA333: m3333: m33.3: 53.: m3%.: m33.: %3333 3333.3 5%.3: 33333 333%.3 m333.3: 333.3 3333.3 %3333 3333 3333.3 3333.3 33%.3 m8333: %333.3- 333%3 33%.3 3333 3333 3333 33333 3%33 m333.3: 3333.3 3333.3- 333%.3 3333.3 %33%.3 m333: : m333.3: 3333.3 m333.3%: 3333.3 33%.3: 53.3: 3333.3 3333: m333.: A333: m333.: m83.: m333.: 533: 3:33 m333%: mA33: m333.3: 53.3: M333: N833: m8%.: 53.: W333.: m33.: 533: m333.3: m33%.33: %3%33 3:33 33333 3333.3 3333.3 m33.3: : 333.3 3333.3 3333 3333.3 :33 - 3333.3 3333.3 3333.3 333.: 333%.3 33%33 3333.3- 3333.3 3333 3333.3 3333.3 333 333%.3 $333 333%.3 m83.3: A333: m333.: m333.3: m333.3: 3333.3 533: m333.: W333.: 3333.3 3333 53.3: m333.: m33%.: m333: 3333.3 m333.3: m333.: m333.3: m33.33: m833: 53.3: A333: m3%.: m333.: m333.333: W333: m333: mA333: 3333.3 333233.333 3333 3%333 3333.3 3333.3 mA333: m33.3: 333 333.3 3333.3 833 333333.333 3333.3 3333.3 3333.3 3333.3 5%.3: 3333.3 333333.333 3333.3 333%.3 333233.333 3333 3333.3 333 3333.3 3333 .333 3.3 3333.3 %333.3 53.33: 333 3%333 3:33 W333: m3: m333.: m333: 3333.3: 3333.3 53.: A333: 3%333 333.3: m333.3: W333.: m33.3: m33.3: 3333 333333.333 : m333: 33%33 m333.3: W333.: 53.3: W333: m333.3: 533: 53.: m333.3: m3333: m3%.3: m333.3: 333 333888333 %333.3 3333.3 A323: 3333.3 %3333 53.: 3333333333 3333.3 3333.3 :33 m333.33: 333888333 3333.3 333%.3 3333 3333.3 m33%.3: 3333 333333833 3333 3333.3 3333 3:33 3333.3 3333.3 3333.3 3333.3 333.33: 3333.3 3333.3 233.3 33%.3: %.3: M333: m333.3: 33333 m333.33: 333%3 3333 333.3: m333.: m83.33: 533: 53.3: M833: m33.3: 3333.3 M333: M333: 53.3: 333333833 M333.: M33.: 53.: 333888333 m33.3: 53.: m33.3: %3333 333833333 53.3: mA333: m8%.3: 33333 NOV337 333%.3 3333.3 3333.3 W333: %3%3 nAOmSE-vav 3333 3333.3 33%33 : n$333-va 3333 333%.3 3333 3333.3 : 3333.3 vav 3333 3333.3 m333.33: N03233:? 3333.3 3333 33333 NOV337 3333.3 3333.3 333%.3 m33333: 3333.3 3%333 3333.3 53.: mA333: m333.3: mA333: 3333 : m333.: m333.3: m333.: 3333.3 333.3: 5%.3: 53.3: W333.: 33333 m333.3: 533.3: m333.3: 3333.3 m33.: 53.3: m333.3: m333.: m333.3: m333.3: 33333 Nemzn-vav m333.: mA333: 53.: 3333.3 3333.3 %33.3 3%333 "E3333 33:33 m3%.: 3333 M323: 333333 %333.3 3333 333%.3 53.33: "E3333 3333.3 3%3%.3 333.3 333 m33%.3: 3333.3 €33.33 3333.3 3%333 333333 3333.3 :333 "E3333 3%333 3333.3 333.3 m83.: "E3333 3333.3 3333.3 3333 A333: 3m33%.3: m333.3: m3333: 333 53.33: 33 m33.3: m3%.: mA333: 3333.3 A33 53.3: m333.3: m33.: m833: 3333.3 m8%.3: ,3 m333.3: W333: %3333 ,33 m83.3: m3%.: m33.33: 3.3 m333.3: m333.: 533: 3333.3 A33 m333.3: 533: m333.: 3333 -3 333%.3 3333.3 3333 m33.3: 3333.3 -3 -3 -3 -3 dz 3333 3333.3 3333.3 m3%.3: -3 .32 dz 3%3%.3 333%.3 3333.3 3333.3 m3%.: 3333 333 53.3: -3.32 3333.3 3333.3 33%33 .2 33%.3 .2 33%33 3333.3 3333.3 m33%.3: .32 33:33 3333.3 3333.3 33%.: 3088 38.8 33.8 32.: 38.3: 3%.: 33.8 33.8 38.8 38.: 32.8 3S8 388 38.8 3388 383: 3%.8 333.: 2 E83 333 82% 333 @883 as: £33 E? 35% 33 E? @838- $8.» 883 $83 :02 523 8:: .2383 38.8 38.8 388 38.0 883:- 38»: 38.8 32.8 38.: 3E8 3%.: 33.8 33.8 $83358 338 33.0: 388 3E8 38.8 38.8 38.8 :53 33.8 388 33.8 E33 38% 3:: 33: 58% 883 833 863 we»: 33.3 3%.» 88": 83.3 $83 $83 Sm? 883: E8: 58.8 38.8 3mm: 88.0- 33.8 388 3wm8 38»: 338 388 3%.8 38.8 3%.8 38.: 33.8 338 38.: 38.8 338 33.8 33.: 33m: M83: 383 36333.883333.883333.838333:83333883333.:~8338888.38:E81333: 68% 3:88&233383333238 33.8 $83 £83 8383 88E 33 SEN 8st Em: 3m: 832 SEN $8: fig 88; 833 3mm8 33.8 883 52 38.8 3%.: 3%.: 3%.8 32.8: 33.8 338 98.0 38.3: 3:8 3%.: 3E8 38.8 3&8 33.: 33.8 3%.: mmm: mama 3%3 N33: 83$ :83 38 3mm8 3x8 583 352 NEE 33.8 N833 823 332 N22 @383 88: .833 EE 3me mg: $93 38.8 33.8 38.3: 38: 3%.: 33.: 338 M3023%.m8fiog3mm88wzmficum: 33.8 33.8 33.: 523 388 3mm.mm3oo.3::$.m3883033038 33»: 338 3388 33.: 3E8 3%.8 33.8 38.: 3%.: 33.88 88.0- 38.8 38: 383 08: 0:: N83 083 an? Ma; 882 8&3 N82 SS8 momma $8.» 3w: 38% 833 momma E32 $33 323 3%.8 332 3&8 33.8 33%: 3mm: 338 38: 3:8 33.8 38.3: 33.8 3388 332%?3E:883336.358 3%.8 38.8 38: 32.: 38.8 3388 338 3%.: 33.8 33.3 3S8 83: 3383 33: 38: $93 3%? 303 23% 38833 RS.» : 882 085 am: 3383 $8: :3; SS8 888% 33.8 832 38.8 38.8 338 38.8 3%.: 38.8 mom? 3838 33.8 38.: 3%.8 3:8 38.8 33.8 3%.: 3:8 368 3&8 ENE 35.08 33.8 332233 338 3%.me 383; $58 Show 38: $8.8 momma 9:3; M88"? @033 $38 :8.» 53 38% 383 $38 882 :83 $8: 33.8 $23 89$ 3308 3%.: mg? Ezmagm 338 338 33.: 3&8 332353 3:8 332233 Ezmagm 388 3322.33 won.N :euegaam 32.38 £2338 cm: 3%.8 333.8 32.8 "hazagoam :fim 3838 388 38.8 3%.: 33.3: 33.8 358 $88 33$ $88 N8": $03 88.0- "Emachooam 83w 8383 882 3838: 888 8%.» 832 8&8 53 3038 N33 88:; N83 3E8 33.8 3%.: WSWN 33.: 533 3838 32.: 33.8 3%.8 33.8 3%.8 38.8 30838 38A :EQEEUEm 3&8 :BQEEUEm 33.8 38.8 33.: 338 £02 "Exachomam 38.8 388 3%.: 382 .AOmzm-EV 0%; :93 33.38 88.0- .AOmzn-vav $3; wow: 8&3 8%? 832 ma; 353 883 3328 0mm; 33%: 388 mum? $58 88% 3338 0%; $8: Emma 3338 3:: 38.: 020m 33.8 3&8 3:: 3&8 33.8 .083 n8.755357 33.: 3%.: 388 NOSE-18v 38.: 3E8 £823-13? 33.8 338 3%.: 38.8 $02 nAOmSE-Edv 333.8 338: 3&8 "25:8 338$ £93 33.: 333.3 €28 :0; WNW: 83.8 wt; $8.0- am? 3:88 3% 33.8 3%.: 3832 N83 $83 am? 333: $03 883 38;? 33% 38% 3838 E"; .88: #83 38.8 am 338 38.8 3?: 3%.: Eva33.838333.88%.N3Q: 38.8 353cm 35:8 3538 £538 3:8 35 38.8 3%.: 3E8 082 ,8 33.8 3mm:8&3386183338 23233.:mmwm.m3$8$8.188$3333835338»:83:23:8838am38.:3mw.m33.3w:3833389533S8 3801338333 3:38: ,S 338 33.8 33m: 38.8 N82 388 "8 3S8 338 38.38 832 -3 38% :53 32.8 03: -3 -3 -3 -3 .oz 83-3 .2 $88 mm: 083 2:3 80me 93% $83 mama .2 35.8 -3 .2 833 882 Mai 333.88 88.0 52 83% 832 $83 88% 3%.: 38.0. 52 833w m8: 883m x33: A53: mpm: 5%.: m$3.: Ammo: A333: W833: A33: mA33: x83: m93.: Am: 33.: mam: A33: 338.3- :33 3:33 3333333:333333.333333333333333.3:323%33.83333323323.183: m333%: 33: 3333 33% 333.133.:3333333:3333333333 333 333 E33 NEE 3353 383.1833: $83 3333 533 333 $333 33% :33 333: 53.: 3:3 W93.: W3.: A83: 33.8 38.: m$3.3: m33.: m5»: 5%.: § 333: 338 W33.: :3: 3.: WS: mG3,: 53.5 3333533: 3333 E3 m$3.: 33.: 3333 32: 3333 333: :33 333 33.1333:333.1333:33333.3:333353333333mat:3333333:333353.333333: 32: 88.3- omen.» :333 333 3333 33 3333 33:; $93 89% 339% m83.: M3.: 88.3- 5%.: £3: 33: $3.:833.3-32:33233.3:8333333333333:33.13333:3393533: 32%: 33: A51: 53.: R333: 33.: m53: m83.: M83.: WAS: mp3: 3333 E33 333 32: 332% 33%: 3333 33.3 fine333333.833.133.33 339% 2333 332% 3933 332% 33: 3323 333.8 383 2:: 3333 333: 53.: m3.: W83.: mam: A33: m$3.: 5%.: £3.33: 332 53.3: A3,: A33: m83.3: A33: A333: 3%.: 333 8333 ~83 33.33333 5; mews:383A333:38333.583.13.33 29% 5333: 383333333333323: mag: 833 3%: 333: 33333 333 3333 333: 33:; 333 333: m3.: 3333 53.3: W3.: 5:: 53.: 53.: x83: 33.3: Amos 53.3: 3%.: mg: W83.: 3:: 53.3: E3 3333 3%.» 3333 :3333,833,283: 333.133.:333333.: 3333 3333 53.3: 33: mom: 933 333 :3: 3233 333 3: 333: $3.» 383% 3:: A32: 53.: 3333 m:3: 33.: 33: A3,: A33: 33.33: x32: 33.: AK: m33.: 33.: 33.: 33.3: 333 3303 233 32: 333 :3: 333333333.133: 333: 3333 3333 2%: 33: 3833 3333 933.133: 333 33 3833 Ammo: 333.183: A333: 393 A533: 33.: :33 A33: W5.: A33: mso: A3,: $3: W933: Amos 33: W33.: W833: 33233.33 333 3323 33233.33 3333 83: :3353333333333: 33233.33 3933 $333 333 m83.3: 33233.33 3%333 33: 3333333333.233:333.1333: 33233.33 @333 3 33%: 33 3333.3 33: 333 333:1: 33333.: W333: WS: 33: £33: 33: :33: 53.3: 383 3:3: 533: $3.3: 33: m3%.: 33 33: 53.3: E33: 3333 333383833 3393 233 3333 333% 333883333 2333 32: 8333 33333 S33 35% m:33: 3333 333: 333% 3383- 3233 @333 333.3333333353: 33.» 33% 33.: 3333 x33: mE: 5333: A333: A33: M33.: 33388383mNon/323-137 53.3: 5:: 53: :33 333823333 A333: ii: 53.8 33:$93Afidmvwmowmmafi:E3x333:3333.13:333353332333333333333.: 53.3: 333383833 33.3: m$3.3: 33 32: 333883333 883 53.3: mag: A2,: 3533 A32: nAOmSE-Env :33 323 339% 3.33 33%: 33333 333 29% 53.33: 333; 33:3 333% 88.3- 33; 3383 W83.: 38.3- 33333 333 3333 A23: 3333 A33: 33.: 5:3:333.233.0333 323: .AOmEQ-vav 33.: W8:: 33333m§:33333§3.: 3.8323 383 33.: 33.: 53: 3:33 NOSE-EV 53.3: 53.3: 53.: 53 m82: nAOmSE-Env W23.: 33.: 233 33: .AOmzn-EV 3:: m83.: A33: :33 A333: €3.33 3383 33 383.1233: 3533: €3.33 33333 33%: 3:338 3333 333 3333 mso: 35:33 3833 N33: :33 A33: 383.3 33: €3.33 3:33 8333 88.3- "25333 3333 3333 333 53.: 333 $33: 33 meg: WE: W833: 2333 33 W333: 333: A333: 383 33 £33: 3333: 333: 3.333 33 3333 ,3 £33: 3:: WES 333 mane 33 333: £33: m8:: 33 333: W85: m3.: 3333: 38.3 -3 3333 3333 333 ASE: 383 -3 823 83: 3:33 3933 £25 -3 2333 $33 533: -3 -3 -3 .32 .32 .2 :33 .oz 3333 33:; 3333 m5.: 3333 .32 3333 9333 :3353333333333333x333:3233332333.133:23333333333333.:233333.:2333 5333: 833 .oz $333 33%.» 333 53333: WO 64460 38.8 38.8 388 380.8803 38.8 3R8 3E8 38.8 32.8 3:8 38.8 338 3%.: 398 3&8 3mm: 3N3 M332 $83 883 Roma OR; 583 88.3w 032 E: Ga? 33¢ 83E 8st 853 am: RN: 38.88353 350.0. we: 35% am? 38.8 32.: 38.8 3%.: 338 38.8 338 32.8 33.: 338 33.8 388 3%.: 3&8 338 33.8 358 38.8 3R8 3%.: 33.: 338 com? 382 333 853 E83 E33 388 SE.» 388 $33 823 mg: 8a? 893 0mm: Mag $3 cm": 38%.» mg; 8m: 8:; 38% 36.: 33.8 3%.: 3%.: 88.8 32.8 338 338 398 3$8 5838.82%833: 33.38 3&8 3E8 33.: 38.8 3R8 3%.8 3%.: 33.8 338 3%.: 38.8 $8.0- 882 mm? Emma 53 383 $02 $me 338 33.88233338331238 38% Seam 802 M58: $33 88.0- am: 8%.» $33 0%: 8%.» $83 3K: $03 388 38.38 3%.: 3an8 3%.: 33.8 3%.8 383 33888.832.8Rood33.88318.va 338 3:88 3R8 338 36.: 33.8 388 3%.8 3mm: 3%.: 3%.: 888:.138 33: 33.8 $03 :3? $33 $03 08"? $33 883 ms; 3338 ~83 New: 8&3 83-3 $8.» 83% 08: E? 83$ $8.5 :33 3:58 89$ 823 38.: 3&8 88% 388 38.: 33.8 33.: 3:8 3%.: 3E8 3%.: 33%: 3028 33.8 338 3%.: 38.: 33.: 3%.: 33.883.32.313332.: 33.8 3038 8&3 33.8 ES 3%.qu 32.8 083 :3.» 303 E33 «83 $83 comma $3 883 05.0 $3 392 83: 2%.» $83 E8: 3%.» 893 5%.» $2 9%? 33.38 3%.: 33.8 3%.: 88.0- $32 3%.: 3wm8$3w 388 E? 33.: 3a.: 33.8 338 38.28 38.8 3&8 3%.: 3333 33.8 33.8 3%.: 33?: 33.: 3%: 38.38 M333 $3.5 cage 832 083 :32 32.08 so: 882 E? 38% #3: 9&3 $53 Emma $8: $st £93 EN? 38.3 $33 533 $33 33.: 33.8 338 3%.: 38.8 338 38.8823 328 802 Emma 33: 33.8 38.8 338 33.8 3%.8 388 3338 33.8 3%.8 38.: 338 202 38.8 38.: 36.: $83 $8.0- 3322.33 $1;338momow33.838838.323338 893 3%; 332333 338 29% $88 N93. 33.3 Ezmagm $38 m3: 823 083 335 3322.33 Sow ms: N32 38% an; aw: m8? S2; 3338 max; 9%: 853 338 333 3%.: 3%.8 8&2 3322.32 Nae/32.3% 2333:3835 0:3 38.88 33.8 38.8 3&8 3:8 35.8 N82 3E8 338 38.: 32.8 33.8 3%.8 3%.: 338 N83 338 3:: 38.8 SEN 88.0- $93 "Emachomam 8me 303123 38.8 332 Emma 3%.: 33.8 3:88 88% EN: Nwmms 83m 3398 883W N8: mom: 338% 38w :8; 803 mot; 3328 88w 8%.» 033 38".: 338 38.: 38.8 3%.: 338 3882 "Exachomam 283W 338 358 33.8 3&8 Roma ".asacbuam 823 38.8 3%.8 388 38.8 239883335 38.8 33.8 3&8 3:8 E33 "huauachooam 3338 33.8 3%.: £08m 38.: 38.0 NOSE-333V 3.53 32 3m§8 NOV357 89; M33; $83 338 nA8353? :33 an? 083 Emma 38.38 Nemzn-vav 23.3w ms: :3": 2:? 38.88 083 $8; 853 88% 3:: Show N83 83$ 33.8 88.0. 33.8 3%.: 3?.8 883 33.: 3mm.8$mo.w 38.3 £83 38.: 3E8 338 38.0: 0:2 3%.; 388 388 33.8 833 .AOmSQ-vav 338 3%.: 38.: 3%.8 8&3 38.: 388 30m: 383 38.08 8 NOmSQ-vav ENE $53 38% 38.28 3538 "3538 $03 £33. 338 £538 83.3w one: ES 333 3:: 33.38 Emma 32 353 3538 $88 8:3 so: 3538 momma NE: N83 3wm8 3538 503 $03 383 3G,: 88.0- 3?.8 3K 38.: 338 a: 33.8 3%.8 338 33 33.8 a» 388 3E8 3E8 33.8 RN? an 3338 388 3%.: 38.38 mmoma ,E 3S8 3:»: 33.: 38.38 0:3 an 32.8 3%.8 3%.: 33.8 Emma -3 :83 3%.: 88.0 -3 .oz $88 NE? 3328 -352 :33 :33 $03 52 883W 8%.» mam.» mg? 33.8 -352 $wa was m3: 35% 3028 -3 as; £83 3:»: -3 .oz cmmmw «mam.» .oz 88% 353 53 £8138 98.0 33.2 33.38 33.8 33.2 33.3- 33.8 3%38 33.8 33.2 33.8 33.8 %%%%% 33.38 38% 23.8 33.2 33.8 33% 33% 33% 33% 33% 33.38 33% 33% %%33.833.13.38 33.8 %%3%% 3%%.8 %%2%% 33% %%%%% 33% 39% 3%: 39% 33% 33.3- 3%%% 33.3- 33.2 33.8 33.8 3%%.8 33.8 39:38 33.8 33%.: 33.: 33.2 33.8 33.38 33.8 33.8 39% 33.3 33.38 3%%.8 33.2 33% 239% 32% 33% 33%.: 33.8 33% 33% 33% 33% 33% 39% 99% 33% 3%%%% 33% 33% 33.13.3332 39%2 33.2 33% %3%%% 38".: 33.8 33.8 33.8 %3%%% 33.3 33%.8 33.2 3:8 32.2 3%%.8 33.8 32.2 3%%.8 3:8 33.38 33% % 33.38 38.8 93%% 333.3 32% %39% 33.8 33.8 33% 39% 33% 33% 35% 33.38 39% 33% 33% 33% 33% 933% 33.8 33.2 33.8 33.2 33.8 3%%.2 328 33% 32% 33.3 328 33.8 33.8 3%%.8 33%.8 %3%% 3%%.8 33.2 33.8 33.8 33.2 33.8 %3%% %%%%% 39% 33.8 33%.8 33.8 3%%%% %%%%.o 33.3- %%%2% 33.3 33.8 33% 38% 33.3- 33% 3%%% 39% 33.8 33% 33% %3%%% 23: 35% 33% 33.38 33.8 39% 33.2 33.8 33.8 33.8 33.2 33% 33.8 33.2 33.8 33.2 33% 33.2 33.8 3%%% 33.8 33.8 33.8 3:8 39%.: %3%%.83%%33.8 32% 33% 322 33% %%%%.3 32.833:33.833.13.38 33.3- %%%2% :33 33.8 33% 33% 38% 3%%%% 33% 33.8 33% 33% 3%%%% 3:8 33% 39% 3%%%8 33% 39% 33%8 3%%.8 33.2 33.8 3%28 33.2 33% %3%%% 33.8 33.8 3:8 33.2 33.2 33.2 23% 33.8 33.8 33%.8 33%.8 33.8 39% 33.8 %%3%% 335% 3%%%% 393 %%3% 33.3 3:28 3%%% 33.38 3%%% 33.8 33% 33% 38% 3%%%% 33% 33.8 3%%% 33% 33% 3%%% 33% 3%%%8 33% 33.8 33.8 33.8 33.2 %%$% 32% 33% 32.8 33.38 33.8 39»: 33.8 3%38 33.8 33.2 33.2 3%%.8 36.8 33.8 3%38 %%3%% 3%%%% 33.8 33% 323.33% 33% 33% 393 33% 353.3% 33% 33.3 33%.: 353.3% 3%%% 33% 33%.:2 353.3% 3%%% 33% 33% 33.2 3%%% 33% 2%%% M: 39% 3%%%8 3% 33% 33%8 33% 33.8 33.8 33.8 33%.: 33.2 33.8 32%.: 33% 33.98 33.8 33.8 33% 392.8 33.2 33.8 %%3%% 33.8 3323.33 33.8 3%%.8 33.8 353.3% 33.8 33.2 33% 3323.33 33.8 33.233%33.333.233.38 23% 3323.33 5388383 33% 99% 33% 33% 39% 5:83:83 33% 33% 3%%.8 "$38233 %%3%% 33% 3:8 "$382303NOSE-18v 33% 38% 32% 39:8 33.3- %9%%% 33% %3%% 33.8 3%%%% %%3% 33.8 3%%%% 33% 33.2 33.8 3918 3%%.8 398 33.2 33%2 %%3%% 33.38 33.8 33.8 33% 33.8 33.2 3.3.2 33% 338 "$388383 33.8 323.8 33%%8 33.3- "$382303 33.8 33.2 33% "assessam 33.8 93%% 23388383 NOV357 33% 32% 39% 39%8 Nev-293V 32% 33.3 3%%% 3%%.8 39% Nemzm-vav 33% 32% 3%28 33% %3%% 33.8 3%%% nAOmzm-Tav 23% 33% 33% 3398 Nemzn-vav 33% 33% 33.8 38% 33.8 33.2 33.8 3:833% %%3%% 33.8 33.8 33%: 33% 33.38 33.8 3%%.8 33% 33.2 33.2 %%%%% 3:8 33.2 33.2 33.8 33.3 33.2 33.8 %%3%% NOV-2:357 33.2 %%3%% nAOmSE-Edv S 33.98 3338 33% 3% 35:3 39% 933% 33% 33.8 33% :3 33% 33% 33.8 33.8 :3 %%%%% 33% %3%%% "238% 93% 39% 38% 3%%.8 3533 833% 233% 33.8 €538 39% 3:8 £538 3% 33.8 33.8 338 %%3%% %% 33.8 33.: 33.38 323% 3%%%8 3:38 33% 3% 3%28 33% ,3 33.8 33%.8 33.32 3% 398 32%.8 33%.: %3%%% n%% 33.8 33.8 33% 3% 33.8 33.8%%%3%3%%.8%%3%3%3.8 %3%%% 3 -3 -3 -3 -3 -3 -3 -3 -3 .32 323% 33% %%3%% 3338 .2 33% 33% 33% 33.38 33% 33.8 .32 %%3% 33% 3%%.8 .oz 33% 33%332389.233.2331 %%%%% 33.32 39% 52 33% 39% 332% 33.38 .2 33% 33% 33.8 52 33% 33% 338 .32 388 %38.~8~8%38.888%3-.8m-m%38.888338888838821.238888838.8 88.8- 38.8 38.8 33~8 388 38.8 38.8 3888 o~ow~ w~8~ 8888338.888338888335888%388 88338.85582338888.128 388 3388 38.8 38.8 3-.8 38.8 888 88% mzms 8~E 888 88% 88: 88% 388 88.8- 88% ~83: 8:3 83% 38.8 38.8 38%8 88.8- 88: 3%~.8 38.8 38.8 3838 ~8%%.~ 388 388 38.8 38.8 38.8 38.8 388 38%8 38.8 33.8 88% 3888 E8.~ ~82 2~8~ 38.2 8 m8": 38: 85% :83 88% 88.8 8%: 8%: 38% 88% 3:8 38.8 38238.8 88.8- -o~3 3:8 3-.8 88.8- 3388 38.8 388 388 38.8 38.88 38.8 38.8 88.13.88 88~ 38.8 38.8 38.8 3888 882 888 ~82 388 888 ~E~s 888 88.» 88% $~m~ ~83 88: 83: 882 3m~8 38.8 33.8 38.888 8~%.~ 88.8- 88.3 38.8 38.888.18.88 38.8 38.88 3:8 38.8 32.8 388 38.8 8:338.888.~38,888,188 32.8 38.8 358 88: 882 388 %: 882 28% 32.28 ~33 588 :88 8~E 88% a~%.~ 888 88% o~8.~ ~E~ 8%%.~ 888 :2: 38.8 38.8 .888.1838 38.8 38.8 38.8 88% 38.8 28838.88 3:8 3m~8 38.8 38.8 38.8 38.88 38.8 38%8 38.8 3888 832 3888883838 8.88 %%8.~38.838.13.38 88.» 88% 8~%.~3¢~+883.18888 88.8 38.8 on: ~33 38.88 88: 8m: 88.8 m%%%.~ 383 388% EM: 88: -o8~ 388 88% 885% 88% 38.8 3808 38.8 32.8 33.8 38.88823o~888%33888% 3:8 3~88 38.8 38%8 32.8 38.8 388 3:8 38.8 38.8 888 2%; 85% 883 ~83 ~88 388% 38.88 8%: 38.88 83: 88% 88.8 88% 888 88% 5%: 88% 8~8~ 38.8 38.8 38.8 338 38.8 388 38.8 88% 36.8 582 88% 388 38.8 38.8 33.88 368 3m~8 38.8 38.8 32.8 8%: -8.~ 3328.88 83: 88883388 3328.88 3:3 828% 88.138388 3322.88 8:3 88% 38.88 3328.88 ~333 38%8 88; 88% 88.8 3:38 38.8 88% ES 88% ~23 m8: 8%8~ 38.8 38.8 388 36.8 388 38.8 882 3838 ~8m~ 3328.88 38.8 38.8 38.8 3328.88 885% 3328.88 388 38.8 3E8 328 32.88 88%.» 838~ 8:": 28% ~83 3~o~8 :88 888 38.8 88.8 388 ~8~.w 88% 833 88.8 888% 38.88 883 ~82 88% 38.8 3w~8 23882583 38.8 33.888.38-38.318? 53:538.; 888 388 358 88338.88 "Exachomam 885% 38.885%38.883188 38.8 38.8 w~$.~ "$382538 38.8 38.8 w~$~ 38.8 "$352888 388 38.8 38.8 ~:m.~38.8$~m~38.888.~358E8.~38.888~3:8~8238.8838~38.888.18.88 "unsechooam 3888 38.8 583 "hmaoaohooam 38.8 3~88 38.8 883 %8~.~ $~8~ NOmSQ-vav 833 38.883.18.28 Nags-EV 838.8 883: nAOmEQ-Edv 88.8 888 38.8 .AOmSQ-vav 85% 88%32.883188 38.8 88.8- 83% 28% 8:: 88% 38.88 ~88w 88% 38.88 38.8 8%? 88% 38.8 38.8 38.8 3~88 32.8 38.8 88338.88 388 36.8 8~8~ 38.8 28~ 3818 .AOmSQ-vav 38.8 3:8 38.8 38.8883 m~om~ nAOmzm-Env 38.8 38.8 m8m~ nAQu-SE-Ezv 3:8 3E8 388 883 88: S8.~ ".538 88% £538 :88 ~83 £538 88.8 8%: 38.8 35:8 -8% 38.8 582 38.88 32.88 3538 28.8 88% 888 3538 838% 88% 38.8 3838 38; 888 28% 3:8 388 ,8 3:8 885% ,8 33.8 32.8 £8~3o~8 8 38.8 38.8 888~ ,8 38.8 88~ 38.8 8 38.8 38.8 388 388 888 38.8 3a 38.8 38.8 m~8.~ a; 388 33~8 32.8 88% m8? 88% 358 -3.2 88% 388% 38~8 -3 88.8 888 -3 -3 -3 -3 -3 .82 ~83 88: .2 32.8 .2 883 E8.» 38.8 M88: .2 :83 88% $88 88% 3888 88.8- 88.8 52 :88 38.8 .2 8:8 c883 88% 2012/071385 W38%: A58 A888 mso: W8%.: W8.: A88: W8.: 53.: 85%: mA9»: W8%: 99% 80%: 888.128 88.0- 89% 88% 88% 89%: 88% 88% 85% 88% 89% 89% 88% 98% 88% 89% 88% W8%.: W8%.: 58%9 88.8- W88 W39%: 88.188 858 8%.: W8%: 58.9 W88 88.: W8%.: W8%.: 88.8888: m8%: 88% 28% 89% 588: 88% 98: 88% 85% 89% 85% %%5% 88% 88% 89% 38% 88% 88.8 m8%.: m8%.: 58%: 58.8 59%.8 89: 58%: m8%: ME»: 88%: 898: m89%: 59%: A9»: W88 88%: %8%% 88% 88% 98% 98% 88% 83% 88% 89% 58% A99888%55.8:85%8088888898: 89% 89% 88% 88% 89% 8%%% %%8%m89888% 88.8 55%: 88% W80%: A88 W88 58%: m858 WS»: A88 A88 W8%: m8%.: A88 W88 58%: 59%: 8%.: 55.8: m8%.8 88%: 88% 98% 88% 88% 88.18.88 %%8% 88% 88% 89% 88% :9% 88% 88% 835% 89% 88% 88% 985% 88.8 m8.8: 5 58.8 W88 A98: 83.: W8%.: 3%: A88 83.: W85%: mQ98 A998 58.8 58.8 88.8 58%: 80.8: 599% 88% 8.8 88% 88% %%9%58.888.18.88 88% 88% 88% 88% 88% %%8% 98% 88% 88% 88% 88% 88% A998 m8%.: :8% 58%: 8%.: 8%.: 858 8%8 80%: 58.8 m8%.: 85%: 58.8: M88 58.8: 58.8 m8%: 58%: 88% 89% 55.8: 88% 998% 88% 8%: 598% 88.8- 58% %98% 88% 28% 88% 88% 88% %%%%.8 89%: 83%: %%9% %80% 8%.: 88.: 58.8 8%.: 83%:88%895888.188 A88 588 58%: 8%.: W35%: A88 W38%: 5:8 A88 A88 8%: 38828 88% 888 W88 38828 98% 88% 88.8288 388988 88% 8%: 89% 88% 38888 88% 88% 88% 988 98% 88.8 88% 898 88% 88% m8.9 58.8 89% W39%: W39%: W898 W388 W89%: W8%: W3%: 88%5%:88.18.888838.: 38828 W39%: 8%.: 28%288885885:88%58,888.18: 38828 m8.9 8%.: 5%.:88%588888.128:88.18.9888%58.82%385885:83:88 388988 55.8: W28%: W88 M88 388988 8%.: 535888 88% 88% 8:8 "$882988 88% 89% 28% "3888588 88% 88% 89% "$382988 88% 29% 28% "$382308 :%8% 88% "$882588 580% 88.8 88% %9:% 38%: 88% W88 5%: 88% m2%.8 858 m3%.: M38%: m8%.8 m8%: mE8 58.8 58%: 858 5%.: 898 m89: 5888388 98.8 W858 88.188: 88.0- "5882988 858 58%: .AOmzm-EV 88% 88% M88 Nemzn-Tav 88% 88% 88% %%8% 89% m8.98 88% 399% 88% 88% 88.8 85%: 89% 88.8 88% 82% 998% 88% 88.0- W98.: W8%.: 88% 5%: 58.8 n$895.37 W35%: 8:: A98: Nemzn-EV m8%.: m898 59%: nAo%:E-_§v W2%.: 8%: 88.8588 88.0- .Ao%zm-_§v 8%.: m8%.: 39%: n$855357 W8.: W8%: Nemzn-Tav W8%.: 588 €28 88% 88% 55%: 35:8 88% 98% 88.88.8838 88% 88% 88% : 3538 £538 885% %59% 88% 35:8 88% 88% 598 85% 88.8 58%:88%85:83:88 95:8 88.0- 3538 88% 89% m8%.:89% m3.388%9188 88% 88% 35:8 8 W88 W8%.: %8%% ,8 mE8 A588 53%: 58 A98: m8%.: W8%.: 88% ,8 mE8 58.: W8.: ,8 W58 A88 88.188: 88% 8 W88 W83%: 8: : ,8 W88 m8.9 W39%: ,8 858 58.8: -3 88% 98% 55%: -3 88% 88% 88% -3 99% 898% 88% A898 -3 %8%% 59% 28% 8%: -3 38% 88% 88% 58.8: -3 -3 -3 .oz 52 .2 52 .2 .94 89% 88% 88.1588: 88% .2 88% 88% 89% 88.18%: 52 88% 2012/071385 %.: mew: 5%.: - 8mg Ami: 32.: man: "are m2%.: W2%.: mAR: m3%.: m8%.: A38 5% 89% at? £2: 2%? 23% 8%.183: $3.0 m5: ES 39% 39$ Em: 8%:AK:omowfiawmxawa 83m AS: mg: 52: 3%.: AS: 39% m80.: 3w;5%.:Sow.mfiw.:ommw.~33.825330:33:33waivwmmvm32:35:18.: 3:: Rafi5.98%.18:£9255: 53: mso: 33: Sonméfi: maw: m5: 5:18.: 3%.» 33% 8%.» 33% E8.» $sz 38% %.: Evficowgogwm $8.» «3% $53 WEE Ammo: mam: ENE $8.12»:NmmmfiWE.:%§.~A~®: 5%.: 83: M80.: AB: "3%.: mam: 53.: do: Maw: $.08 Room: 083 Ammo: 9%.: 88.0- 8%2 88% 33 32% Ewes 0%: :03 39% 08: mmmms N22 8%: 38.0: 53: $3% 88.0- WE}: AK: AR: 5%.: AS: £2: 5%: W83.: m5: AS: mac: £2: %.: Em: 85% m8? a3: NE% ANS: 29% m8:: mom? ENE 38% 52: 033 03% 92-2 ma: 3%% 5: $3.18.:oawm m5.: mam: m3%: mg: mac: mac: 53.: 35.13:: 359% WEE mg: 5%.: ASE: 5%.: A03: $3: we»: 9%: wows 9%? Sham 38: 3&% Eom.mx$.ovwm$.m WE.» ammow 03% £38 $02 0%: m8? Smom 831%: mmows 83% £3 38: M6%: 5%.: mAS: ME: £3: fix: 88.0- 88.0- 5%.: 083 meme maw: an: #0.: WE: 5%.: éw: £3: x3: Rafi: 88% 3%: ma; SO: memo: mete £0: .82: N83 éweowwm%xmm.e mama: 333 28.» 38.0. OS: 392% 33.13.38 MKS; 033 gem 3%: 33% 5%.: ANN: m8%.: m8%: 38.: A3: 231mm: £3 8%? 53%: E2 Am: 5%: Ag: m83: was»: wmom.mém.w: Am»: A3: maw: AS: AS: 8%? 332333 3%: R53 Mao? 332853 53 38% 339553 S33 W3%: 332353 $33 gigs: 3%.: 35:63 3:3 33% - 30% Ea% Ezmqam 88% $93 : 332253 $3% 092% mafia met: £5: £5: 5%.: 5%.: 3%: EN: 03% mam: 933 mag: £2: A2»: 3%.: 3%.: mGo: A2: mam: watm "$888325Mega-.57 £2: 38% 3%: 2&3 2&3 am? 5w: 083 mag: egg $32 33.8 «8% 6:.» Nwmow 23.0% 33% 953 Bax 89% wmowm meow: met: 5%.: ASS: usuafiuam Maw: mso: AR: N82 usoeohuam "ES: "he-«actuam mE: Ame: x38 mews "$382325 meme m5»: 50.: mam: mam: 302 38% $3 $3 NomSn-cav 332% Em: $0253.:offimave "$383.38.;Nomzn-vav 23% 5%.: 38% N83 Ba: mommaéoév 88% gawm $0333.:$3138 wmmflw 3%: $33 23% Enm ROE: A58 AR: mso: W8%.: At: m8%.: 932%5&330353: SEN Nemzn-gv AS: Maw:Em?gowmfiwgméo: manqmfimdzéa 3.: nAOmSE-vav 53.: mac: HEQEEBEV-Nov-2:357 A8,: W83: ,AOmSn-vav m3%.: AK: W8:: oamMega-.57 Ame: Ammo: $02 3538 8N3 3%? 85% 8%: €038 93% $33 353cm 3%; £3: 35:8 9:3 éw: 88.0- "3538 9&3 583 03:13.2: 3538 53% 85% ".538 983 32% 35% 3538 88% 83% 33.8 ns: 55.: man: 5%.: 88.0- ,2: 5%.: mam: SW: d3 in: $3.35.: 2%: ,2: Ache 32.8 i: mac: 63.: meowmémé235%.:8%:59:29.13:mwowfiaw:05%itsoomw.mxmv.ovomom.méo.%3E%.%ANS: "m3 £98 3%.: a: £3: 3%.: 332: E: A03: Ram: RSN -3 52 35% :02 Ewwm m8:: -3 a: -3 -3 -3 -3 .2 $$% E 89333.3: 88.0 52 23% 0&3 in: .2 M33 38% 3318.: NS? 05% 38% $3.139: -3 52 3:3 52 mmofiw N30: E913:05.18.: -3 83% 35% 33% .oz 52 omwmw Roma ASS $33 ":33 Am; 3%.» £58 wave :02 AS: mama 50: RES Sam meow: woo? A38 2%; 38.0 N22 52; 9:3 woo? Sm? 53: 805 AME $82 in: $3.138 A9»: 53.8 ANS: A2,: ~33 :39 was.» 3N2 m2: mead 8mm.» A25 Smms A25: was Emma $312.5 Sam x33 528$ 03: A85 mews 533 Ame: gas égv 2&5 wags we"? A38 Sm: $36 owvms 88.0- 55.3 #32 Mafiméoé 3me 203 £me RES @3me A30 fig Amie mam: E: want 53.0 $3.5 as; A38 SE 5:3 momma Rmms 8N2 x85 mwmms $me A3: ~83 mamas mam: Amos Sta i2; A3,: gas £03 £33 32:2: gas A3,: m2: 39% 25.3: 8:: 9%: 83.» Emma A38 E03 @250 Bigot:88.132 9&3 99% 82.0- x89 "ems mg? 52V wave xii A33 m3: A25 NS? mam: A83 am: 22% gas 39: 0%? N82 Emma x33: A31: o8: Raf; 083 Ammi £0: $8.0- 53 5:»: mewe 838 €35 8319,338383.:Nfioismdfimwmfin:89$ E238 023 mama: mesa 5:33 mm: 803 €me N23 o3? 5R2 awom :35 mom: x35 Magi A533 Ezmqam £di A03: gem Aid AS: meme wave "$3558.;Nomznéav mmwmw "EM: mama acqfiami magma; 88.0- 53 A33 Emma NEE okms $03 éms E: ACNE 5%: :soeéuam g": 8312.3$6.13: wag 53.: 5m: 853 53; m22V A89 émé $03 55.3 Emma "5&8 $8.0 £3 53 Amt: so: momma Some $2; SE mam: -_év momma €on mews Am: 0:2 A89 A2: Gm: A29 A38 "Emzomuwiédz $53 mews 5:"? M503 88.0 35:8 83w Show £2: as? :53 $8.0- $02 93; 533 Mam: £23 mwsfiams "5&3 53.: 5: WARS A39 293 AS: in: xmflé mama moms N33 mafia 083 wmog 88.0 -3 .2 35w 2%.» maps Roma 3&2 88.0 2012/071385 £358 mwasomfioo E .823 8: 8: 8s CE :oflfiwmma .93; "E «mm 65 "8 9 9 M 3 8 .5 3% E OE 352 mzz SEE @6885 @5888 E $42 wofiomw S CE H8 8:38am @6808 3288 com: 88 choquo z new?» as dml :meo a mm: 6: :SSE 2388 mm m m m m m m E m m m mupfiggofifi "M m m m m m m E m m m BEES mm m m m m m m m m m m mafia: m mm m m m m m m m m m m 0552:: m m QB R E N £0 £0 £0 - o £0 £0 : £00 £0 8 -onomz -onomz 333 2358 mo N C-m EQW _o-m £06 mam EQW 6-0 6% 6 m6% _O-m Eva 6% 6a £06 6-m wag/0:8 Q M m v h a .o - - - BEL Bash $859800 IN IN Z a a: Ta: a: 3: 0-x: a: ME: a 03: WO 64460 -100— .82? OE OE £3; " a S E mom 08 % o o I I I w S Cam £7 838st moEmem E? $38st mS/ mS/ mS/ mS/ CE E S 05 S 07w moamummmm an: wE E22 com mom .2 2+3: o 03 2+3: 08 8a mm m m m E m m m m m m m m m 5.2% m «M m m m m m m m m m m m m m m m mm m £6000 m m m £0 mu £0 £0 £6 £0 £0 £0 £0 £8 mm m m m m m E m E E E E E E E E Hm E6 .8634 -o m a m N 3E6 mo m o £0 565-46 E -Nmo Nmoumo .96 m m m m m m I momo m m m m m m m ax "5 "6 mm We. 65. 6"5.
I WW Wow - I 6-m I 6% _o-m _O-m 5m I m m mugm £06 EQW £06 Eva £9m 6% _o-m am mm- 60%- Wm o 6a m I m m 2 M: a E .oZ 2-": NZ: -5 - - - m E-§ 2-5: 2-": :-§ a: E 8-5: 35: NE: min a: mi: -101— .82? WEEK: $2282 E E .68< 6-3% £3; E .>Im 5 9 8 8 A W "N5 .8 nest .8800 mzz E .888 £388 328% 338% mzz E 2 E E a 8 .08 memo: m .oz-m<6 .oz-m<6 wE6666< .826 «m I - - - I I I 6a mm : m a m m m m m m -666 1me m m m 5-2% m «M m m m m m m m m m m m m m m m mm 6666 @2666 6666 DEE/66 "mg/66 : m m m m m v v m N :66N :66N :66N :6 mm m m m m m m m N£6.26 m :6 £6-26 A266 E m m m m : m m m m m $562 £6-m £6-m mmUIW m m _ _ n 6 - W6. 6- m mmI 6-m m6-m X 6-m 6-m £6-m 6-m 6-m 6-m 6-m 6-m 5% 6-m 6-m 6- £6-m 6-m m6-m W6. m mmI m £6-m .o 8-36 S5: mm o3: om 3-5: mm m3: $-36 mm cm R mm I - Z a: E I6 -a Is Id Is a a a : : 3-5: 2}: 2012/071385 -102— .82? Ages Emofiwa $9508 BEAN 30% 983 £3; 8.2;» A «Nb .8 SE. E22 8 .08 mama: wamoia @3588 38$ MSE moamummmm 03 03 5" wfigooo< .826 0B 03 "3 E9 EH :3 Si _O-m £06 .oZ EVANS WO 64460 -103— 58.8 82a 3318.2838553.8mtg52.8$85538$5355.:E$.m5:.80mmo.m58m: 5%.8 5:28 53.8 53.8 5R8 538 55.8 5&8 5%.: 5%.: 52.28 5:88 5K8 53.8 58.8 mommm $92 mmmos 588 88.0 mom? $02 83.5 285 Save $528 SEW wow: 882 ENS $3 at: 5: 88.0 58.88 56.8 53.8 $25 58.28 5&8 58.: 55.: 53.8 5%.: 55.: 58.8 5%.: 53.: 58.8 $3.138 538 5:8 53:8 5858 :03 8&3 53.8 mg: E; ME? $35 $2.5 582 ES 80% mmgm 893 am? $83 883 8%? Emma 55.: 58.8 53.8 83m 5%.8 588 53.8 53.8 53.8 58.8 56.8 58.8 53.8 53.8 585.8 53.8 5&8 538 58.8 80% 852 58.: 38mm am? 8%? 3&5 mm: 52 $2 88$ 8&3 NW3; 882 8885:8386 3mm 803 8m: 28.5 5&8 558 5N8 Ema 5&8 538 5%.: 52.8 5&8 5%.: 5:8 53: 58.8 5%.: 5R8 5&8 5mm: 58.28 538 5R8 Eco Saw 883 5%.: :86 $0? NE? $3.5 $8.5 833 :52 Emww coo; 25% Sm: EOE 8me 885 8:5 £85 538 58.8 538 53.8 New? 53.8 5%.8 52.8 58.8 5&8 5a.: 558 53.8 558 58.8 5&8 5&8 5028 5:88:353.8as"?5mm580mmm.m58.833158 53.8 53.: 52.8 5S8 23.0 imam 8%: 5%.: 35$ 8mm? 83m 23.5 82.5 $8.0 E83 owmod 88% maow m5; :81 mg: 083 $85 E: $8.5 53.8 5A8 5:8 imam 5528 52.8 5&8 558 53.8 5&8 588 538 5&8 538 55.8 5:18 53.8 3.0138 53.: 5K: 58.: 58.8 2&2 55% 853 53.: $35 88% 5%? $3 $85 $858 WES $8.0 am? 38¢ £2 SS5 $th $0255.: 53mm 385 mg: 35:5 53.8 538 5&8 Sam 53.8: 53.8 58.88 5&8 58.8 5&8 538 53.8 5:: 55.: 53.8 5wm8 58.8 52.8 58.8 58.8 5S8 New; 525.5% Egg was 5&8 885% ES 033 wt: 8&3 m8? 830 55;; 88.0 at}. wmgw $3 833 5:3 8:3 385 Rm: 88.5 5S8 58.8 53.8 083 85m 53.88 cm" 5:8 E2 5%.8 58.8 5S825.1%.883553.8 55.8 588 58.8 5%.: E2 538 $2353 58.8 5S8 58325:: 52 5%.: 502: 52.8 5%.: 538 53.8 3de ussectuamx :53 025 58.8 53.: 083 :3 :3 $93 :3 53.8 :52 58888.0- "Sauaohuam 88; :02 «ms: R30 383 88.0 5:3 $va Em; Emmi mega momma $85 853 Mam: 538 53.8 momma omwom 5&8 53:: Esaetam 58.8 58.8 m3;5&832.1%.:$25528 5K: 538 5%.: 5:8 sosagaam 58.28 53.8 52.8 58.8 5:8 "5388.865 5x8 53.8 5K8 58.8 52.: 5E8 253 "hazachooamfi 825-55? N23 835 5%.21835 nA 58.8 53.8 owe/5-557 $52 :82 8:? 803 E02 3:; $8.0 mg: 083 383 5518.8 3:: :53 NS; some 82: 3mm: 023 58.8 5R8 5E8 $2 NS; $03 58.08 .Amonov 5A8 588 5&8 53:8 58.8 5S8 ,Aaonov 55.8 5&8 538 598 .Amonov 538 5mb8 5&8 5:8 5R8 mmmwd Om2:-_wav SSW EN? 5%.: 52.8 5558 5888 85% 55:55-35 083 am; £9: £30 woe; $8.0 2-55 mg; $3 Emma 8:: 55 wage 5585132 898538 Mag 58.8wNR.N5Nm.8$9353,835,198£358.:8mm?535180.138835538$555588331%.:3353.838m i: Man: 23.5 5%.8 % ".528 35:8 52.8 5%.: 23 of am 852 335 528 588 52.8 5%.8 588 5&8 5&8 53.8 5%.: 5828 52.28 5%.: 53.8 588 58.8 58.: 53.8 88.0 45:275-? .3: 6.": 352543: .2 Raw mg? 58.8 5A8 55.5 53.8 52 8&3 .2 Saw 852 8&2 89: $3 0:3 $2.0 .oz Raw mmfiw 029m 9&5 R25 .2 3m; $83 28% ms": 8:: 8&3 5.85:8 52 WO 64460 —104— :»: Ag: mat: Amos N83 0&3 032 mama 0%; $03mammfiwmalmv:32.1%.:Sobiflmgfitqwmavemoomm 55%: Amos Rama: $8.0- 0?? 32¢ Ema 88.5 :: M32: $38 $8.0 WSW: v33 5%.: mA3,: 5%.: 83m 33 $3.133: 513: A3,: 93.13%: m8:: :93 Mao: ammm an: 88.0- E50 Room $8.5 m8? AK: 5%.: 53.: m6:: mE: meme Ammo: 3me 8:2 £2: Ego mac: 8sz Emma Smog 653 56.: A3,: meme 2mm: $03 $312.5: 5%? was: E03 52.8 8mg $318.: £3 $02Amweflibowfiswws 5V3: A02: 53.: 83." Na? ME: 833 fin: mso: 5:: £2: 53%: 5%.: 5:1: men? 03$ mmowmmsgm: 032 S$.m§w.8%£.m mag 55c: 55.: £30 9&2 0%; 0:3 2525;: max: 25.0 588 A8,: $8.188: #82 game Ammo: 5:}: x38 ANS: 083 ES meow: 333 £3: :33: mg; $3; 33aAmmdwomofism:N8323:3352:30.13:mg;53.:m2;Rowemwflaxmwe8m;A3808;A8,:0Efi89: $0138 39: $8.0 mag: AME: 55.: 520130522Amwaomixmwe$8.12.: mam; 55: 32: ~83 £35 $de 5:: m3:: A3: $3M 3N3 m6:: wwmflw meme £3 38.0- £28.53 AWE: m8%: £39: $8.0- 38¢ go; 3:5 825 Em? Age 39% 53.0: £22.53 53.3 A8,: fig: 23m ANS: mso: m3:: map: ng 302 3%; meme 333 88.0- usaaitoamfi m$.m mews: 88.0- "Emachooamfi $05; EN; $8.12.:2313.8 £2 88.0 58.8 55:: RNMN 5%.: mawe Raw: Roma Ami: fine 5%.: 5%.: 55:: 83w Emma AS: £93 38.0 omznéav 5%; 5:9 Rama: $8.0 omEEEV wwwflw wmmwm comma $3.0 mso: 55.: 835 58.: 53.8 5%.: 38a 59:: 5:: 5a.: 3313.052: mE: AR: wags $me 5%.: $8.0 mom; 303 AS: 083 $53 Ex; o3; 52: 083 &8 mew: 3M2 5:»: Age 352563: 52%: 83m "628: 5%.: s§2£5¢§ AB: mam: 38a $313+: 58.8 N8; 39% $915.8 52: ESQ New; 52 25% 55.0: 0:3 MRS .cz mag 83m ANN: 9&3 88.5 5%.: 2012/071385 -105— £859? .823 .83; E E E E E E .8 5 8 .8 .8 8 8 8 8 am .8 SE. 0232 82-2888 23%me 33822 Tvzwmmi 8 E 8:28am .888 .888 .888 .888 .888 33.895 82-95 .oz-m6 <6 .8 m-mm-Ewoa 566 E-mm-BwoooE mmvos n-mo-meoS mmoa o-Nv-novoa m-mo-owmoa 0583 o-mo-mamvfi wéw-Ewooe EwoooE 8:95.3E .888 .888 .888 .888 .888 .888 .888 .888 .8800 .888 .888 .888 .888 33.889 .oZ-m (Int-1), Solvent: >, Spectrometer: 250 MHz 8.8851 (2.85); 8.8810 (2.90); 8.0597 (3.16); 8.0531 (3.03); 7.3468 (0.43); 4.6887 (0.86); 4.6601 (2.73); 4.6314 (2.77); 4.6028 (0.92); 1.9535 (0.37); 1.8201 ); 1.7915 (15.84); 1.6816 (1.04); 1.3985 (0.39); 1.3699 (0.41); 1.3263 (2.32); 0.9654 (0.63); 0.9398 (2.11); 0.9121 (0.74) (Int-2), t: , Spectrometer: 250 MHz 8.8501 (0.70); 8.8470 (0.81); 8.8429 (0.82); 8.8399 (0.72); 8.0975 (0.87); 8.0908 (0.87); 2.7950 (0.75); 1.9777 (16.00); 1.3467 (1.18); 0.9585 (1.01); 0.9309 (0.35) Step 2: Synthesis of tert-butyl chloro(trifluoromethyl)pyridin—2-yl]methylpropyl}carbamate (Int-3) — 112 — F C CI F C CI 3 P 3 W / CN —> / L LCH3 N N M 0 CH3 H3C CH3 H3C CH3 (Int-2) (Int-3) 270 mg of 2-[3-chloro(trifluoromethyl)pyridin—2-yl]methylpropanenitrile (Int-2) (1.08 mMol), 470 mg (2.16 mMol) of di-tert—butyl carbonate, 256 mg (1.08 mMol) of nickel-(ll)—chloride-hexahydrate were stirred in 7 mL of methanol at room temperature. 284 mg (7.6 mMol) of sodium borohydride were added portionwise. After 2 hours of stirring, 20 mL of ethyl e were added to the reaction mixture, followed by 5 mL of an aqueous solution of sodium bicarbonate. After separation, the c phase was washed with 5 mL of an s solution of sodium bicarbonate, dried over magnesium sulfate, filtered and concentrated to yield 283 mg (48%) of crude material, which was purified over silica gel to produce 185 mg of desired product tert-butyl {2-[3-chloro(trifluoromethyl)pyridin—2 -yl] methylpropyl} carbamate (Int-3).
(Int-3), Solvent: , Spectrometer: 250 MHz 8.6142 (1.38); 7.8087 ; 7.1968 (0.42); 5.3003 (0.41); 3.5212 (2.11); 3.4946 (2.03); 1.6795 (0.65); 1.4510 (3.37); 1.4297 (18.21); 1.3873 (1.28); 1.3387 (16.00); 1.2821 (0.82); 1.1813 (0.64); 1.0122 (0.48) Step 3: sis of 2-[3-chloro-S-(trifluoromethyl)pyridin—2-yl]methylpropan—1-amine hydrochloride (Int-4) (not isolated) F C CI F C CI 3 P 3 0 / L LCH3 —>- / XHCI N N 0 CH3 N NH2 H3C CH3H H3C CH3 (Int-3) (Int-4) according to P10, prep. example 7, page 60 and Step 4: sis of N- {2-[3-chloro(trifluoromethyl)pyridinyl]methylpropyl} oromethyl)benzamide (Ia-93) F3C CI F3C CI \ \ o 1 l CF3 / XHCI —> / N NH2 N M H3C CH3 H3C CH3 (Int-4) (la-93) according to P10, e.g. prep. example 2, page 56, in a one-pot reaction 2012/071385 —113— In a similar manner the final products ); (la-95); (Ia-96); (la-97) and (la-106) can be prepared.
Synthesis of N— {2-[3-chloro(trifluoromethyl)pyridinyl]methoxyethyl} (trifluoromethyl)benzamide (Ia-1 1 1) Step 1 : Synthesis of N— {2- [3 -chloro-5 -(trifluoromethyl)pyridinyl]ethylidene} (trifluoromethyl)benzamide (Int—6) F C CI F C CI 3m0 CF3 3m0 CFS / / (Int—5) (Int-6) 2.00 g of N— {2—[3—chloro—5—(trifluoromethyl)pyridin—2—yl]ethyl}—2—(trifluoromethyl)benzamide (Int—5); (known from ), were dissolved in 20 mL of methanol. 1 mL of concentrated bleach was added to the reaction mixture at room temperature. The reaction mixture was stirred for 24 hours at room temperature. 20 mL of a 1N aqueous solution of sodium hydroxide were added to the reaction mixture which was then extracted twice with diethyl ether. The combined organic phases were dried over magnesium sulphate, concentrated in vacuo to yield 1.41g of crude product which was d by chromatography on silica gel with ethyl acetate/heptane (3/7 V/V) as eluting phase. 340mg (17%) of desired N—{2-[3-chloro(trifluoromethyl)pyridin—2-yl]ethylidene}(trifluoromethyl)benzamide (Int- 6) were obtained, [M+1] = 395.
(Int-6), t: , Spectrometer: 250 MHz 8.9332 (9.79); 8.9300 (10.02); 8.1058 (10.17); 8.0994 (10.79); 8.0590 (0.59); 8.0405 (4.14); 8.0293 (4.93); 8.0053 (5.61); 7.8799 (4.19); 7.8553 (5.39); 7.8433 (6.53); 7.8254 ; 7.8135 (0.43); 7.7616 (1.08); 7.7531 (2.30); 7.7313 (7.59); 7.7224 (10.49); 7.7082 (16.00); 7.6941 (8.42); 7.6624 ; 7.3731 (2.26); 6.3219 ; 6.2909 (6.05); 6.2819 (6.18); 6.2509 (5.77); 4.6899 (3.46); 4.6499 (3.13); 4.6312 (10.24); 4.5911 (10.09); 4.5750 (10.55); 4.5440 (10.16); 4.5161 (3.62); 4.4853 (3.08); 4.2001 (0.84); 4.1747 (0.34); 3.9138 ; 3.7663 (0.44); 3.5945 (1.93); 3.5203 ; 2.1563 (1.20); 1.7637 (14.75); 1.3752 (2.57); 1.0440 (0.56); 1.0153 (0.88); 0.9906 (2.20); 0.9629 (0.84) Step 2: Synthesis of N- {2-[3-chlor0(trifluoromethyl)pyridinyl]meth0xyethyl} (trifluoromethyl)benzamide (Ia-1 1 1) FC CI N \NJKE: CINJKfi: (Int-6) (Ia-111) 0.16 g of N- {2-[3 -chloro(trifluoromethyl)pyridin—2-yl]ethylidene}(trifluoromethyl)benzamide (Int- 6) were d in 2 mL of methanol. 50 "L of sulfuric acid 99% were added. The reaction mixture was —114— stirred at room temperature for 48 hours. A e of dichloromethane (10 mL) and water (5 mL) was added. After separation, the aqueous phase was extracted twice with dichloromethane. The ed organic phases were washed with 5 mL of water, dried over magnesium sulfate, filtered, concentrated to yield to 0.150 g of crude material, which was purified by chromatography on silica gel to yield 0.107 g (63%) of desired product N— {2—[3—chloro—5—(trifluoromethyl)pyridin—2—yl]—1—methoxyethyl} —2— (trifluoromethyl)benzamide (Ia—111), [M+1] = 427.
(Ia-111), Solvent: , Spectrometer: 250 MHZ 12.1063 ; 12.0712 (1.19); 12.0521 (0.95); 12.0171 (0.38); 11.9822 ; 8.8855 ; 8.1085 (16.00); 7.8954 (0.37); 7.7656 (0.49); 7.2610 (0.36); 6.0372 (0.33); 5.6296 (0.39) Synthesis of 2- [3 o(trifluoromethyl)pyridin—2-yl] {[2-(trifluoromethyl)benzoyl] amino} ethyl acetate (la-1 12) 0 CH FBCm o CF3 F3(KEk/[CI/Cf/o 3 CFs N/ w: a N/ we (Int-6) (Ia-112) 0.16 g of N— {2—[3 —chloro—5—(trifluoromethyl)pyridin—2—yl]ethylidene}—2—(trifluoromethyl)benzamide (Int— 6) were diluted in 2 mL of acetic acid. The on mixture was stirred for two days at room temperature and then heated to 90 0C for one day and left at room temperature for four days. After concentration in vacuo, the crude product was purified by chromatography on silica gel to yield 0.045 g (24%) of desired t 2- [3 -chloro-5 -(trifluoromethyl)pyridin—2 -yl]-1 - {[2- (trifluoromethyl)benzoyl] amino} ethyl acetate (Ia-1 12), [M+1 ] = 455.
(Ia-112), t: , Spectrometer: 250 MHz 8.7470 (0.39); 8.6387 (1.99); 7.9142 (2.37); 7.9078 (2.10); 7.6281 (0.97); 7.6011 (1.38); 7.5952 (1.39); 7.5508 (0.70); 7.5391 (0.62); 7.5255 (1.49); 7.5013 (2.27); 7.4927 (2.11); 7.4625 (1.11); 7.4431 (1.65); 7.4120 (0.74); 7.1939 (0.35); 6.4536 (0.68); 6.2788 (0.95); 6.2616 (1.19); 6.2555 (1.23); 6.2384 (0.96); 4.1809 (0.48); 4.1640 (0.52); 4.1544 (0.51); 4.1375 (0.51); 4.1235 (0.73); 4.1067 (0.74); 4.0970 (0.74); 4.0802 (0.66); 3.8884 (0.67); 3.8658 (1.13); 3.8431 (0.71); 3.8313 (0.54); 3.8084 (0.79); 3.7859 (0.47); 3.4015 (0.59); 2.0705 (16.00); 1.9568 (0.34); 1.1896 ; 0.8053 (0.74); 0.7776 (0.33) Synthesis of intermediates (Ila-15) and (Ila-14): Step 1 : Preparation of ethyl ichloropyridin—2-yl)(difluoro)acetate (Int-7) — 115 — CI CI CI CI \ \ 0 I 0 + I / Br / N Br N OCZHS OC2H5 F F F F (Int-7) To a solution of 56 g (0.246 mol) of 2-bromo-3,5-dichloropyridine in 500 mL of dry dimethylsulfoxide, were added 53 g (0.261 mol) of ethyl bromodifluoroacetate followed by 94 g (0.518 mol) of copper bronze (200 mesh). The beige suspension was heated at 50 °C for 5 hours. After cooling of the reaction mixture, a solution of 44 g (0.328 mol) ofpotassium monophosphate in 280 mL of water was added and stirred for 1 hour. The black mixture was then filtered over a cake of SupercelTM, and the cake was washed three times by 200 mL of ethyl acetate. The organic phases were collected, washed with brine and dried over magnesium sulfate. Evaporation of the t under vacuum gave 57.6 g of brown oil.
After purification by column chromatography on silica gel ne/ethyl acetate 9/1) 40 g (57%) of ethyl (3,5-dichloropyridin—2-yl)(difluoro)acetate (Int-7) were obtained as a yellow oil, (M+1) = 270, R(235MHZ,CDC13) 5 (ppm): - 104.21 (CF2).
Preparation of ethyl [3-chloro( trifluoromethyl)pyridin—2-yl](difluoro)acetate (Int-8) F3C CI \ F3C CI 0 0 N Br r OCZH5 N OCZH5 F F F F (Int-8) Under the same conditions, 47 g of 2—bromo—3—chloro—5—(trifluoromethyl)pyridine, yields 46.7 g (46%) of ethyl [3-chloro( trifluoromethyl)pyridin—2-yl](difluoro)acetate (Int-8) as a yellow oil.
Step 2: ation of 2-(3,5-dichloropyridinyl)-2,2-difluoroethanol (Int-9) CI CI CI CI N OC2H5 N OH (Int-7) (Int-9) To a solution of 10 g (37 mmol) of ethyl (3,5-dichloropyridinyl)(difluoro)acetate (Int-7) in 60 mL of ethanol, were added portionwise at 0 0C, 1.05 g (27.7 mmol) of sodium borohydride. The reaction mixture was stirred below 10 0C for 2 hours. 30 mL of 1 N HCl were then slowly added ed by 500 mL of water. The aequeous phase was extracted three times by 300 mL of ethyl acetate and the —116— organic phase was successively washed with brine, water and dried over magnesium sulfate. After ation of the solvent under vacuum 8.5 g of yellow oil were obtained. After trituration in diisopropyl ether and filtration 6.8 g (80%) of 2—(3,5—dichloropyridin—2—yl)—2,2—difluoroethanol (Int—9) were obtained as a white solid. Mp (melting point) = 56 0C. (M+1) = 228. 19F—NMR (235MHz, CDC13) 5 (ppm): — 105.85 (CFz).
Preparation of 2-[3-chloro(trifluoromethyl)pyridinyl]-2,2-difluoroethanol (Int-10) F3C CI CI \ F3C 0 \ 1 —» | / / N OC2H5 N OH F F F F Unb8) Unb10) Under the same ions, reduction of 12 g of ethyl [3-chloro( trifluoromethyl)py1idin fluoro)acetate ), resulted in 6.8 g (65%) of 2-[3-chloro(trifluoromethyl)pyridinyl]-2,2- difluoroethanol (Int-10) as a yellow oil, (M+1) = 262, 19F-NMR (235MHz, CDClg) 5 (ppm): - 106.74 (CF2); - 63.18 (CF3).
Step 3: Preparation of 2-(3,5-dichloropyridinyl)-2,2-difluoroethanamine (Ila-15) CIm a mN CI CI CI \ \ OH N NH2 F F F F (Int-9) (Ila-15) To a on of 1.3 g (5.7 mmol) of -dichloropyridinyl)-2,2-difluoroethanol (Int-9) in dry acetonitrile under argon, were added 0.744 mL (9.12 mmol) of dry pyridine. The reaction mixture was cooled to 0 °C and 1.06 mL (6.27 mmol) of triflic anhydride were added dropwise in 15 min while maintaining the temperature below 8 °C. The reaction mixture was stirred at 0 °C for additional 30 min. 9.9 mL of a 28% w/w aqueous solution of ammonia (144 mmol) were added and the reaction mixture was stirred at room temperature for 2 days. The reaction mixture was diluted with 50 mL of brine and the product extracted three times with 25 mL of ethyl acetate. The organic phases were collected, washed three times with 40 mL of brine and dried over ium sulfate. Afater evaporation of the solvent under vacuum 1.09 g of brown oil were obtained. After purification by column chromatography on silica gel (heptane/ethyl acetate gradient) 0.65 g (50%) of -dichloropyridinyl)-2,2- difluoroethanamine (Ha-15) were obtained as a yellow oil, (M+1) = 227, 19F-NMR (235MHz, CDClg) 8 (ppm): - 104.80 (CFz). —117— ation of 2-[3-chloro(trifluoromethyl)pyridinyl]-2,2-difluoroethanamine (Ha-14) F3C CI \ F3C CI i/ l/ N OH N NH2 FF FF (Int—10) (Ila—14) Under the same conditions, amination of 1.5 g of 2-[3-chloro(trifluoromethyl)pyridin—2-yl]-2,2- difluoroethanol (Int-10), ed 0.4 g (27%) of 2-[3-chloro(trifluoromethyl)pyridinyl]-2,2- difluoroethanamine (Ha-14) as a yellow oil, (M+1) = 261, 19F-NMR z, CDCl3) 8 (ppm): - 105.48 (CF2); - 62.97 (CF3).
Synthesis of ediate (Ha-16) Step 1: Preparation of 3-[3-chloro(trifluoromethyl)pyridinyl]butan—2-one (Int-12) F3C CI \ F30 CI 0 \ 0 | —» | / / N CH3 N CH3 1) (Int-12) CH3 6.00 g of 1-[3-chloro(trifluoromethyl)pyridin—2-yl]acetone (Int-11) (27 mMol) (synthesis according to P10 and com. av.) and 5.75 g of methyl iodide (40.5 mMol) were diluted in 120 mL of dimethoxyethane. 3.03 g of potassium hydroxide were added portionwise at room temperature.
After cooling, 100 mL of water were added to the reaction mixture which was extracted twice with 150mL of ethyl acetate. The organic phase was washed twice with 100 mL of water, dried over magnesium sulfate and concentrated. After purification on silica, 0.67 g (39%) of desired product 3-[3- chloro(trifluoromethyl)pyridinyl]butan—2-one (Int-12) were obtained, [M+1] = 252.
Step 2: Preparation of 3-[3-chloro(trifluoromethyl)pyridinyl]butan—2-amine (Ila-16) F30 CI \ F3C CI o \ CH3 / —> / N CH3 N NH2 CH3 CH3 (Int-12) (Ila-16) —118— 0.64 g of 1-[3-chloro(trifluoromethyl)pyridin—2-yl]butan—2-one (Int-12) (0.0025 mol) were diluted in mL of methanol. 7.0 g of molecular sieves 3 A 1.90 g (0.025 mol) of ammonium acetate and 0.39 g (0.0052 mol) of sodium cyanoborohydride were added. The reaction medium was stirred ght at room temperature. After filtration, the pH was adjusted to 9 with an aqueous solution of 1 N sodium hydroxide. The reaction mixture was concentrated to dryness and 30 mL of ethyl acetate were added.
The organic phase was washed with an aqueous solution of 1 N sodium hydroxide, brine and water; dried over magnesium sulfate, d and concentrated to dryness. The crude material was ved in mL of 1 N hydrochloric acid and extracted with 15 mL of ethyl e. An aqueous on of 1 N sodium hydroxide was added to the aqueous phase, which was subsequently extracted twice with 15 mL of ethyl acetate. The organic phase was dried over magnesium sulfate, filtered and trated to dryness. 0.21 g (32%) of desired product 1-[3-chloro(trifluoromethyl)pyridinyl]butanamine 6) were obtained, [M+1] = 253.
(Ha-16), Solvent: , ometer: 250 MHz 8.8007 (1.26); 8.7474 (4.38); 8.7114 ; 8.6750 (0.36); 7.9494 (0.94); 7.9165 (5.80); 7.8572 (0.64); 7.2852 (4.01); 4.4592 (0.43); 4.4301 (0.35); 3.7320 (3.86); 3.5142 ; 3.4764 (0.56); 3.4505 (1.77); 3.4238 (3.16); 3.3975 (3.05); 3.3807 (1.53); 3.3561 (2.58); 3.3312 (3.03); 3.3063 (1.80); 3.2810 (0.52); 3.0742 (0.39); 3.0493 (0.38); 2.1316 (7.72); 1.6759 (0.81); 1.6137 (16.00); 1.5889 (2.25); 1.5492 (0.55); 1.5133 (1.30); 1.4535 (4.53); 1.3733 (1.83); 1.3369 (13.49); 1.3099 (13.31); 1.2792 (4.17); 1.2534 (4.91); 1.2219 (4.68); 1.1978 (3.94); 1.1754 (0.82); 1.0772 (12.77); 1.0519 (12.76); 0.9908 (1.18); 0.9655 (1.06); 0.9102 (0.50); 0.8863 (0.66); 0.8671 (0.49); 0.7657 (0.94); 0.7408 (0.83) In a similar manner compound (Ila-24) can be prepared by reacting 1-[3-chloro (trifluoromethyl)pyridin—2—yl]acetone (Int—1 1) and cyclopropylamine.
Synthesis of intermediate (Ila-40) Preparation according to known methods (cf. J. Amer. Chem. Soc. 72, 2804-6 (1950); W0 1984/03278; ; THL 45, 7407-08 (2004)) (IIa40), Solvent: , Spectrometer: 400 MHz is shown in Figure 2.
Synthesis of intermediate (IIa-41) Preparation ing to known methods (cf. J. Amer. Chem. Soc. 72, 2804-6 (1950); WO 1984/03278; ; THL 45, 7407-08 (2004)) (IIa41), Solvent: , Spectrometer: 400 MHz is shown in Figure 3. sis of intermediate (IIb-34) Step 1: ation of 4-chloro(trifluoromethyl)nicotinic acid (Int-11) CF CF Cl 3 3 N O N O OH OH (Int-11) A solution of 2,2,6,6-tetramethylpiperidin (198.8 g, 1.41 mol) in tetrahydrofuran (1.5 L) was added n-butyl-lithium (564 mL, 1.41 mol) dropwise at -78 oC. Then the mixture was stirred from -78 oC ~ -30 oC for 30 minutes. Then the mixture was cooled to -78 oC and a solution of 6- uoromethyl)nicotinic acid (90 g, 1.47 mol) in tetrahydrofuran (2.5 L) added dropwise at - 78 oC, then the mixture was stirred from -78 oC~ -40 oC for 1 hour. The mixture was cooled to - 78 oC and a solution of hexachloroethane (222.5 g, 0.94 mol) was added to the reaction e dropwise. The mixture was stirred at -78 oC for 3 hours. Aqueous ammoniumchloride (1500 mL) was added to the mixture slowly at -78 oC and the mixture was stirred at room temperature for 20 minutes. The mixture was extracted with ethyl acetate (1 L * 3). The combined organic layer was concentrated and the residue was purified by silica gel chromatography eluted with dichloromethane: methanol= 20: 1 to yield ro(trifluoromethyl)nicotinic acid (Int-11) (85 g, 80%) as a brown solid.
(Int-11), Solvent: , Spectrometer: 400 MHz is shown in Fig. 4.
Step 2: Preparation of [4-chloro(trifluoromethyl)pyridinyl]methanol 2) CF Cl CF Cl 3 3 N O N OH OH (Int-11) 2) To a mixture of 4-chloro(trifluoromethyl)nicotinic acid (Int-11) (85 g, 0.377 mol) in tetrahydrofuran (1.5 L) was added F (755 mL, 0.755 mol, 1M in THF) slowly with ice bath. The mixture was stirred at room temperature overnight. Aqueous NH4Cl (500 mL) was added to the mixture slowly with ice bath and the mixture was poured into water (1 L). The mixture was extracted with Ethyl acetate (1L* 3). The combined organic layer was washed with brine, dried over Na2SO4 and concentrated to give crude [4-chloro(trifluoromethyl)pyridin yl]methanol (Int-12) (90 g, 100%) as brown syrup, which was used for the next step without further purification.
(Int-12), t: , Spectrometer: 400 MHz is shown in Fig. 5.
Step 3: Preparation of 4-chloro(chloromethyl)(trifluoromethyl)pyridine (Int-13) CF Cl CF Cl 3 3 N N OH Cl (Int-12) (Int-13) [4-Chloro(trifluoromethyl)pyridinyl]methanol (Int-12) (90 g, 0.426 mol) was added to SOCl2 (700 mL) slowly with ice bath, the mixture was refluxed for 1 hour. The mixture was concentrated and the residue was poured into water (1 L). The mixture was adjusted to pH= 7~ 8 with solid NaHCO3. The mixture was ted with ethyl acetate (500 mL* 3). The combined organic layer was concentrated to yield 4-chloro(chloromethyl)(trifluoromethyl)pyridine 3) (80 g, 87%) as brown syrup which was used for the next step without further purification. 3), Solvent: , ometer: 400 MHz is shown in Fig. 6.
Step 4: Preparation of [4-chloro(trifluoromethyl)pyridinyl]acetonitrile (Int-14) CF Cl CF Cl 3 3 N N Cl CN (Int-13) (Int-14) Trimethylsilylcyanid (TMSCN) (69.3 g, 0.7 mol) was added to a solution of 4-chloro (chloromethyl)(trifluoromethyl)pyridine (Int-13) (80 g, 0.348 mol) and Tetra-nbutylammoniumfluoride (129.5 g, 0.7 mol) in acetonitrile (1.5 L) slowly. Then the mixture was stirred at 20- 30 oC for 2 hours. Thinlayer tography (petroleum ether: EtOAc = 3: 1) showed all of starting material was consumed. The mixture was concentrated and the residue was purified by silica gel chromatography eluted with petroleum ether: EtOAc= 20:1~ 3:1 to yield [4- chloro(trifluoromethyl)pyridinyl]acetonitrile (Int-14) (50 g, 60% from NMR, 39% of yield) as yellow syrup.
(Int-14), Solvent: , Spectrometer: 400 MHz is shown in Fig. 7.
Step 5: Preparation of hloro(trifluoromethyl)pyridinyl]ethanamine (IIb-34 ) hydrochloride CF Cl CF Cl 3 3 x 0.5 HCl N N (Int-14) (IIb-34 x 0.5 HCl) To a mixture of [4-chloro(trifluoromethyl)pyridinyl]acetonitrile (Int-14) (50 g, 0.227 mol) in THF (1.5 L) was added BH3-THF (908 mL, 0.908 mol, 1N in THF) slowly with ice bath. Then the mixture was d at room temperature for 3 hours. Methanol (500 mL) was added to the mixture slowly with ice bath. The mixture was concentrated and the residue was purified by silica gel chromatography eluted with dichloromethane: methanol= 20: 1~ 10:1 to give crude 2-[4- chloro(trifluoromethyl)pyridinyl]ethanamine (IIb-34 x HCl) (20 g), which was poured into HCl-ethyl acetate (300 mL) and d at room temperature for 1 hour. The mixture was filtered and the filter cake was washed with methyl-t-butylether (20 mL*3) and dried to yield 2-[4-chloro- 6-(trifluoromethyl)pyridinyl]ethanamine (IIb-34 x HCl) (14 g, 46%, hydrochloride salt) as offwhite solid.
(IIb-34 x HCl), t: , ometer: 400 MHz is shown in Fig. 8.
Synthesis of intermediate (IIb-35) Step 1: Preparation of 2-chloro(trifluoromethyl)nicotinic acid (Int-15) CF CF 3 3 N N O Cl Cl OH (Int-15) To a stirred solution of 2-chloro(trifluoromethyl)pyridine (50.0 g, 1.0 eq.) in tetrahydrofuran (1.0 l) was added drop wise lithium diisopropylamide (LDA) (44.2 g, 1.5 eq.) at -78 °C. After 2 h dry carbondioxide (500 g) was added at -78 °C. The resulting reaction mixture was allowed to room temperature and stirred for 10 min. The reaction progress was monitored by TLC. After tion of reaction, the reaction mixture was acidified with 1 N HCl up to pH 2 and extracted with ethyl acetate (2 x 500 mL). The combined organic layer was washed with water (500 mL), brine (500 mL), dried over anhydrous sodium sulfate and concentrated under d pressure to get crude product which was triturated with pet ether to get pure 2-chloro- 6-(trifluoromethyl)nicotinic acid (Int-15) (40.0 g, 64.6 %).
(Int-15), Solvent: >, Spectrometer: 400 MHz is shown in Fig. 9.
Step 2: Preparation of oro(trifluoromethyl)pyridinyl]methanol (Int-16) CF CF 3 3 N O N Cl OH Cl OH (Int-15) 6) To a stirred solution of e 2-chloro(trifluoromethyl)nicotinic acid (Int-15) ( 40 g, 1.0 eq.) in THF (400 mL) was added BH3-THF (266.6 mL, 1.5 eq) at room temperature. The progress of the reaction was monitored by TLC. After 16 h the reaction mixture was concentrated under d pressure to remove THF. The resulting reaction mixture was diluted with 10 % NaHCO3 (500 mL) and extracted with ethyl acetate (2 x 500 mL). The combined organic layers were washed with water (500 mL), brine (500 mL), dried over anhydrous sodium sulfate and the solvent was removed under reduced pressure to get crude [2-chloro(trifluoromethyl)pyridinyl]methanol (Int-16) as light yellow liquid, 32 g (85.5 %).
(Int-16), Solvent: , Spectrometer: 400 MHz is shown in Fig. 10.
Step 3: Preparation of 2-chloro(trifluoromethyl)nicotinaldehyde (Int-17) CF CF 3 3 N N H Cl OH Cl O (Int-16) 7) To a stirred solution of [2-chloro(trifluoromethyl)pyridinyl]methanol (Int-16) (80.0 g, 1.0 eq.) in dichloromethane (700 ml) was added pyridinium chlorochromate (160.0 g, 2.0 eq), um dioxide (240 g) at room temperature and stirred for 4 h. The progress of the reaction was monitored by TLC. After completion of reaction, reaction mixture was filtered through silica gel bed and washed the bed with excess 90 % ethyl e in pet ether and filtrate was concentrated under reduced pressure to get crude 2-chloro(trifluoromethyl)nicotinaldehyde (Int-17) as yellow liquid (70.0 g, 88.3 %). GC-MS: m/z 209 ([M]).
Step 4: Preparation of 1-[2-chloro(trifluoromethyl)pyridinyl]nitroethanol (Int-18) CF CF 3 3 N H N Cl O Cl OH (Int-17) (Int-18) To a stirred solution of 2-chloro(trifluoromethyl)nicotinaldehyde (Int-17) (70 g, 1.0 eq.) in nitro e (700 mL) was added sodium hydroxide (6.7 g, 0.5 eq.) at room temperature. The resulting reaction mixture was heated to 100 °C and stirred for 2 h. The progress of the reaction was monitored by TLC. After completion of on, the reaction mixture was concentrated under d pressure to remove nitro methane quenched with ice water (500 mL) and extracted with ethyl acetate (2 x 1.0 L). The combined organic layer was washed with water (500 mL), brine (500 mL), dried over anhydrous sodium sulfate and concentrated under reduced pressure to get pure 1-[2-chloro(trifluoromethyl)pyridinyl]nitroethanol (Int-18) (65.0 g, 72.0 %).
(Int-18), Solvent: , Spectrometer: 400 MHz is shown in Fig. 11.
Step 5: ation of 2-chloro[(E)nitrovinyl](trifluoromethyl)pyridine (Int-19) CF CF 3 3 N N NO NO 2 2 Cl OH Cl (Int-18) (Int-19) To a stirred on of 1-[2-chloro(trifluoromethyl)pyridinyl]nitroethanol (Int-18) (27 g, 1.0 eq.) in dichloromethane (270 mL) was added thylamino pyridine (13.5 g, 1.1 eq.) followed by drop wise addition of acetic anhydride (13.5 g, 1.3 eq) at 0 °C and stirred for 15 min. The ss of the reaction was monitored by TLC. After completion of reaction, the reaction e was quenched with ice water and extracted with dichloromethane (2 x 200 mL). The combined organic layer was washed with water (200 mL), brine (200 mL), dried over anhydrous sodium sulfate and the solvent was removed under reduced pressure to get crude 2- chloro[(E)nitrovinyl](trifluoromethyl)pyridine (Int-19) (22.0 g, 87.6%).
(Int-19), Solvent: , Spectrometer: 400 MHz is shown in Fig. 12.
Step 5: Preparation of 2-[2-chloro(trifluoromethyl)pyridinyl]ethanamine (IIb-35) hydrochloride CF CF 3 3 N N NO NH x HCl 2 2 Cl Cl (Int-19) (IIb-35 x HCl) To a stirred solution of NaBH4 (16.0 g, 4.2 eq.) in tetrahydrofuran (125 mL) was added BF3 etherate (125 mL) at 0 °C. The resulting reaction mixture was allowed to room temperature and stirred for 15 min. 2-Chloro[(E)nitrovinyl](trifluoromethyl)pyridine (Int-19) (25.0 g, 1.0 eq) in tetrahydrofuran (125 mL) was added to above on mixture at room temperature. The reaction mixture was heated to 70 °C and stirred for 2 h. The resulting reaction mixture was allowed to room temperature and stirred for 16 h. The progress of the reaction was monitored by TLC. After completion of reaction, the reaction mixture was quenched in ice water (200 mL) and extracted with ethyl acetate (3 x 200 mL). The combined organic layers were washed with water (1 x 100 mL), brine (1 x 100 mL), dried over anhydrous sodium sulfate and the t was removed under reduced re to get crude amine. The amine compound was dissolved in ethanolic HCl (50 mL) and stirred at room temperature for 2.0 h. The on mixture was concentrated under reduced pressure to get crude 2-[2-chloro(trifluoromethyl)pyridin yl]ethanamine (IIb-35) hydrochloride (15.0 g, 58.3 %). x HCl), Solvent: <[D6]-DMSO >, Spectrometer: 400 MHz is shown in Fig. 13. — 132 - Biological Examples Meloidogyne incognita - test Solvent: 125.0 parts by weight of acetone To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, and the concentrate is diluted with water to the desired concentration. s are filled with sand, a solution of the active ingredient, a suspension containing eggs and larvae of Meloidogyne incognita and salad seeds. The salad seeds germinate and the seedlings grow. Galls develop in the roots.
After 14 days the nematicidal activity is determined on the basis of the percentage of gall formation. 100% means that no galls were found; 0% means that the number of galls found on the roots of the treated plants was equal to that in untreated l plants.
In this test, for example, the following compounds from the preparation examples showed an activity of 100% at an application rate of 20 ppm: Ia—3, Ia—43, Ia—46, Ia—47, Ia—50, Ia—70, Ia—92, Ia—93, Ia—110, Ia— 113, Ia-114, Ia-122, , Ia-127, Ia-l31, Ia-137, Ia—l40, Ia-l4l, Ia-142, Ia-l43, Ia-147, Ia-l48, Ia- 153, Ia-154, , Ic-l, Ic-2, Ic-7.
In this test, for example, the following compounds from the preparation examples showed an activity of 90% at an application rate of 20 ppm: Ia-170, Ia-172, Ia-174, Ic-5.
, Ia—196, Ia-211, Ia-212, Ib-47, Ib-58, In this test, for example, the following compounds from the ation examples showed good activity of 70 % at an application rate of 20 ppm: Ib-50, Ib-51.
In this test, for example, the ing compounds from the preparation examples showed an activity of 100 % at an application rate of 4 ppm: Ic-8.
Cooperia curticei—Test (COOPCU) Solvent: dimethyl sulfoxide To produce a le ation of active compound, 10 mg of active compound are dissolved in 0.5 m1 solvent, and the concentrate is diluted with "Ringer’s solution" to the desired concentration.
Approximately 40 Cooperia curticei larvae are erred into a test tube containing compound solution. After 5 days percentage of larval mortality are recorded. 100 % efficacy means all larvae are killed; 0 % y means no larvae are killed. —l33— In this test for example, the following compounds from the preparation es showed good activity of 100 % at an application rate of 100 ppm: Ia-l, Ia-4, Ia—S, Ia-6, Ia-48, Ib-47, Ib-49, Ib-SO, Ib-51, Ib-52, Ic—l, Ic—7.
In this test for example, the ing compounds from the ation examples showed good activity of 90 % at an application rate of 100 ppm: Ib-48, Ic-59, Ic-60, Ic-75.
In this test for example, the following compounds from the preparation examples showed good activity of 80 % at an application rate of 100 ppm: Ic—26, Ic—58.
Haemonchus contortus—Test gHAEMCOL Solvent: dimethyl sulfoxide To produce a suitable preparation of active compound, 10 mg of active compound are dissolved in 0.5 ml solvent, and the concentrate is diluted with "Ringer’s solution" to the desired concentration.
Approximately 40 Haemonchus contortus larvae are transferred into a test tube ning compound solution. After 5 days percentage of larval mortality are recorded. 100 % efficacy means all larvae are killed, 0 % efficacy means no larvae are killed.
In this test for example, the following compounds from the preparation examples showed good activity of 100 % at an application rate of 100 ppm: Ib-47, Ib-49, Ib-SO, Ic-l, Ic-7.
In this test for example, the following compounds from the preparation es showed good activity of 90 % at an application rate of 100 ppm: Ia-l, Ib-48, Ib-Sl.
In this test for example, the ing compounds from the preparation examples showed good activity of 80 % at an application rate of 100 ppm: Ia-5, Ia—6, Ia—48.
In this test for example, the ing compounds from the preparation examples showed good activity of 80 % at an application rate of 20 ppm: Ib—52.
Patent

Claims (20)

Claims:
1. Compounds of a 5 3 R3 R4 O Xn 6 6 N N 5 F F R R5 m 2 4 wherein X is selected from the group consisting of halogen, nitro, cyano, hydroxy, amino, -SH, -SF5, - CHO, -OCHO, -NHCHO, -COOH, -CONH2, -CONH(OH), 2, (hydroxyimino)- C1-C6-alkyl, C1-C8-alkyl, C1-C8-halogenoalkyl having l to 5 halogen atoms, C2-C8-alkenyl, C2-C8-alkynyl, C1-C8-alkylamino, di-(C1-C8)-alkylamino, C1-C8-alkoxy, C1-C8- noalkoxy having l to 5 halogen atoms, C2-C8-alkenyloxy, C2-C8-halogenoalkenyloxy having l to 5 halogen atoms, C3-C8-alkynyloxy, C3-C8-halogenoalkynyloxy having l to 5 halogen atoms, C3-C8-cycloalkyl, C3-C8-halogenocycloalkyl having l to 5 halogen atoms, C1-C8-alkylcarbonyl, C1-C8-halogenoalkylcarbonyl having l to 5 halogen atoms, - CONH(C1-C8-alkyl), -CON(C1-C8-alkyl)2, -CONH(OC1-C8-alkyl), -CON(OC1-C8- alkyl)(C1-C8-alkyl), C1-C8-alkoxycarbonyl, C1-C8-halogenoalkoxycarbonyl having l to 5 halogen atoms, C1-C8-alkylcarbonyloxy, halogenoalkylcarbonyloxy having 1 to 5 halogen atoms, C1-C8-alkylcarbonylamino, C1-C8-halogenoalkylcarbonylamino having l to 5 halogen atoms, -OCONH(C1-C8-alkyl), -OCON(C1-C8-alkyl)2, -OCONH(OC1-C8-alkyl), -OCO(OC1-C8-alkyl), -S-C1-C8-alkyl, -S-C1-C8-halogenoalkyl having l to 5 halogen atoms, -S(O)-C1-C8-alkyl, -S(O)-C1-C8-halogenoalkyl having l to 5 n atoms, -S(O)2-C1-C8- alkyl, -S(O)2-C1-C8-halogenoalkyl having l to 5 halogen atoms, (C1-C6-alkoxyimino)-C1- C6-alkyl, (C2-C6-alkenyloxyimino)-C1-C6-alkyl, (C3-C6-alkynyloxyimino)-C1-C6-alkyl, (benzyloxyimino)-C1-C6-alkyl, benzyloxy, -S-benzyl, benzylamino, phenoxy, -S-phenyl and phenylamino, n is 1, 2, 3 or 4 and if n is 2, 3, or 4 then the substituents X may be the same or ent, R3 and R4 are the same or ent and are selected from the group consisting of hydrogen, halogen, cyano, hydroxy, amino, -SH, -CHO, -COOH, , -CONH(OH), -OCONH2, (hydroxyimino)-C1-C6-alkyl, C1-C6-alkyl, alkenyl, C2-C6-alkynyl, C1-C6-alkylamino, di-(C1-C6-alkyl)amino, C1-C6-alkoxy, hydroxy-C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkyl, C1- C6-halogenoalkyl having 1 to 5 halogen atoms, C1-C6-halogenoalkoxy having 1 to 5 halogen atoms, C2-C6-alkenyloxy, C2-C6-halogenoalkenyloxy having 1 to 5 n atoms, C3-C6- alkynyloxy, C3-C6-halogenoalkynyloxy having 1 to 5 halogen atoms, C3-C6-cycloalkyl, C3- C6-halogenocycloalkyl having 1 to 5 halogen atoms, C1-C6-alkylcarbonyl, C1-C6- halogenoalkylcarbonyl having 1 to 5 halogen atoms, -CONH(C1-C6-alkyl), -CON(C1-C6- alkyl)2, -CONH(OC1-C6-alkyl), -CON(OC1-C6-alkyl)(C1-C6-alkyl), C1-C6-alkoxycarbonyl, C1-C6-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, -OC(O)-C1-C6-alkyl, - C1-C6-halogenoalkyl having 1 to 5 halogen atoms, -NHC(O)-C1-C6-alkyl, )-C1-C6- halogenoalkyl having 1 to 5 halogen atoms, -OCONH(C1-C6-alkyl), -OCON(C1-C6-alkyl)2, -OCONH(OC1-C6-alkyl), OCO(OC1-C6-alkyl), C6-alkyl, -S-C1-C6-halogenoalkyl having 1 to 5 halogen atoms, -S(O)-C1-C6-alkyl, -S(O)-C1-C6-halogenoalkyl having 1 to 5 halogen atoms, -S(O)2-C1-C6-alkyl, -S(O)2-C1-C6-halogenoalkyl having 1 to 5 halogen atoms, benzyl, benzyloxy, -S-benzyl, -S(O)-benzyl, -S(O)2-benzyl, benzylamino, phenoxy, -S-phenyl, -S(O)-phenyl, -S(O)2-phenyl, phenylamino, phenylcarbonylamino, 2- chlorophenyl-carbonylamino, 2,6-dichlorophenyl-carbonylamino and phenyl; R5 is selected from the group consisting of hydrogen, cyano, -CHO, -OH, C1-C6-alkyl, C1-C6- halogenoalkyl having 1 to 5 n atoms, C1-C6-alkoxy, C1-C6-halogenoalkoxy having 1 to 5 halogen atoms, C3-C7-cycloalkyl, C3-C7-halogenocycloalkyl having 1 to 5 halogen atoms, C2-C6-alkenyl, C2-C6-alkynyl, alkoxy-C1-C6-alkyl, C3-C7-cycloalkyl-C1-C6- alkyl, cyano-C1-C6-alkyl, amino-C1-C6-alkyl, C1-C6-alkylamino-C1-C6-alkyl, di-C1-C6- mino-C1-C6-alkyl, C1-C6-alkylcarbonyl, C1-C6-halogenoalkylcarbonyl having 1 to 5 halogen atoms, C1-C6-alkoxycarbonyl, benzyloxycarbonyl, C1-C6-alkoxy-C1-C6- alkylcarbonyl, -C1-C6-alkyl, and –S(O)2-C1-C6-halogenoalkyl having 1 to 5 halogen atoms; R is selected from the group consisting of halogen, nitro, -OH, NH2, SH, SF5, CHO, OCHO, NHCHO, COOH, cyano, alkyl, C1-C8-halogenoalkyl having 1 to 5 halogen atoms, C2-C8-alkenyl, C2-C8-alkynyl, C3-C6-cycloalkyl, -S-C1-C8-alkyl, -S-C1-C8-halogenoalkyl having 1 to 5 halogen atoms, C1-C8-alkoxy, C1-C8-halogenoalkoxy having 1 to 5 halogen atoms, C1-C8-alkoxy-C2-C8-alkenyl, C1-C8-alkoxycarbonyl, C1-C8- halogenoalkoxycarbonyl having 1 to 5 halogen atoms, C1-C8-alkylcarbonyloxy, C1-C8- halogenoalkylcarbonyloxy having 1 to 5 halogen atoms, -S(O)-C1-C8-alkyl, -S(O)-C1-C8- halogenoalkyl having 1 to 5 halogen atoms, -S(O)2-C1-C8-alkyl, -S(O)2-C1-C8- halogenoalkyl having 1 to 5 halogen atoms, alkylsulfonamide, -NH(C1-C8-alkyl), 8-alkyl)2, phenyl (optionally substituted by C1-C6-alkoxy) and phenoxy, or two R bonded to adjacent carbon atoms er represent –O(CH2)pO-, n p represents 1 or m is 0, 1, 2, 3, 4 or 5 and if m is 2, 3, 4, or 5 then the substituents R may be the same or different.
2. Compounds according to claim 1, in which X is selected from the group consisting of halogen, nitro, cyano, C1-C4-alkyl, C1-C4- halogenoalkyl having l to 5 halogen atoms, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkylamino, di- (C1-C4-alkyl)amino, C1-C4-alkoxy, C1-C4-halogenoalkoxy having l to 5 halogen atoms, C2-C4- alkenyloxy, C2-C4-halogenoalkenyloxy having l to 5 halogen atoms, C3-C4-alkynyloxy, C3-C4- halogenoalkynyloxy having l to 5 n atoms, C3-C6-cycloalkyl, C3-C6-halogenocycloalkyl having l to 5 halogen atoms, C1-C4-alkylcarbonyl, C1-C4-halogenoalkylcarbonyl having l to 5 halogen atoms, -CONH(C1-C4-alkyl), -CON(C1-C4-alkyl)2, -CONH(OC1-C4-alkyl), -CON(OC1- C4-alkyl)(C1-C4-alkyl), alkoxycarbonyl, C1-C4-halogenoalkoxycarbonyl having l to 5 halogen atoms, C1-C4-alkylcarbonyloxy, C1-C4-halogenoalkylcarbonyloxy having 1 to 5 halogen atoms, C1-C4-alkylcarbonylamino, C1-C4-halogenoalkylcarbonylamino having l to 5 halogen atoms, (C1-C4-alkyl), -OCON(C1-C4-alkyl)2, -OCONH(OC1-C4-alkyl), -OCO(OC1-C4- alkyl), -S-C1-C4-alkyl, -S-C1-C4-halogenoalkyl having l to 5 halogen atoms, -S(O)-C1-C4-alkyl, - 1-C4-halogenoalkyl having l to 5 halogen atoms, -S(O)2-C1-C4-alkyl, -S(O)2-C1-C4- halogenoalkyl having l to 5 halogen atoms, (C1-C4-alkoxyimino)-C1-C4-alkyl, (C2-C6- alkenyloxyimino)-C1-C4-alkyl, (C3-C6-alkynyloxyimino)-C1-C4-alkyl, (benzyloxyimino)-C1-C6- alkyl, benzyloxy, -S-benzyl, benzylamino, y, -S-phenyl and phenylamino, n is 1, 2, 3 or 4 and if n is 2, 3, or 4 then the substituents X may be the same or different. R3 and R4 are the same or different and are selected from the group consisting of en, n, cyano, hydroxy, amino, -CHO, -COOH, -CONH2, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1- C4-alkylamino, di-(C1-C4-alkyl)amino, C1-C4-alkoxy, hydroxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C3- alkyl, C1-C4-halogenoalkyl having 1 to 5 halogen atoms, C1-C4-halogenoalkoxy having 1 to 5 n atoms, C2-C4-alkenyloxy, C2-C4-halogenoalkenyloxy having 1 to 5 halogen atoms, C3- C4-alkynyloxy, C3-C4-halogenoalkynyloxy having 1 to 5 halogen atoms, C3-C6-cycloalkyl, C3-C6- halogenocycloalkyl having 1 to 5 halogen atoms, C1-C4-alkylcarbonyl, C1-C4- noalkylcarbonyl having 1 to 5 halogen atoms, -CONH(C1-C4-alkyl), -CON(C1-C4-alkyl)2, -CONH(OC1-C4-alkyl), -CON(OC1-C4-alkyl)(C1-C4-alkyl), C1-C4-alkoxycarbonyl, C1-C4- halogenoalkoxycarbonyl having 1 to 5 halogen atoms, -OC(O)-C1-C4-alkyl, -C1-C4- halogenoalkyl having 1 to 5 halogen atoms, -NHC(O)-C1-C4-alkyl, -NHC(O)-C1-C4- halogenoalkyl having 1 to 5 halogen atoms, -OCONH(C1-C4-alkyl), -OCON(C1-C4-alkyl)2, - OCONH(OC1-C4-alkyl), OCO(OC1-C4-alkyl), -S-C1-C4-alkyl, -S-C1-C4-halogenoalkyl having 1 to 5 halogen atoms, -S(O)-C1-C4-alkyl, -S(O)-C1-C4-halogenoalkyl having 1 to 5 halogen atoms, -S(O)2-C1-C4-alkyl, -S(O)2-C1-C4-halogenoalkyl having 1 to 5 halogen atoms, benzyl, benzyloxy, -S-benzyl, -S(O)-benzyl, -S(O)2-benzyl, benzylamino, y, -S-phenyl, -S(O)-phenyl, -S(O)2- phenyl, phenylamino, phenylcarbonylamino, 2-chlorophenyl-carbonylamino, 2,6- dichlorophenyl-carbonylamino and phenyl; R5 is selected from the group ting of hydrogen, -CHO, -OH, C1-C4-alkyl, C1-C4-halogenoalkyl having 1 to 5 halogen atoms, C1-C4-alkoxy, C1-C4-halogenoalkoxy having 1 to 5 n atoms, C3-C6-cycloalkyl, C3-C6-halogenocycloalkyl having 1 to 5 halogen atoms, C2-C4-alkenyl, C2-C4- l, C1-C4-alkoxy-C1-C4-alkyl, C3-C6-cycloalkyl-C1-C3-alkyl, cyano-C1-C4-alkyl, amino-C1- C4-alkyl, C1-C4-alkylamino-C1-C4-alkyl, di-(C1-C4-alkyl)amino-C1-C4-alkyl, C1-C4- alkylcarbonyl, C1-C4-halogenoalkylcarbonyl having 1 to 5 halogen atoms, C1-C4-alkoxycarbonyl, benzyloxycarbonyl, alkoxy-C1-C4-alkylcarbonyl, -S(O)2-C1-C4-alkyl, and –S(O)2-C1-C4- halogenoalkyl having 1 to 5 halogen atoms; R is selected from the group ting of halogen, nitro, -OH, CHO, OCHO, NHCHO, cyano, C1- C4-alkyl, C1-C4-halogenoalkyl having 1 to 5 halogen atoms, C2-C4-alkenyl, C2-C4-alkynyl, C3-C6- cycloalkyl, -S-C1-C4-alkyl, -S-C1-C4-halogenoalkyl having 1 to 5 halogen atoms, C1-C4-alkoxy, C1-C4-halogenoalkoxy having 1 to 5 n atoms, C1-C4-alkoxy-C2-C4-alkenyl, C1-C4- alkoxycarbonyl, C1-C4-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, C1-C4- alkylcarbonyloxy, halogenoalkylcarbonyloxy having 1 to 5 halogen atoms, -S(O)-C1-C4- alkyl, -S(O)-C1-C4-halogenoalkyl having 1 to 5 halogen atoms, -S(O)2-C1-C4-alkyl, -S(O)2-C1-C4- noalkyl having 1 to 5 halogen atoms, C1-C4-alkylsulfonamide, -NH(C1-C4-alkyl), N(C1-C4- alkyl)2, phenyl (optionally substituted by alkoxy) and phenoxy, or two R bonded to adjacent carbon atoms together represent –O(CH2)pO-, wherein p ents 1 or 2, m is 0, 1, 2, 3, 4 or 5 and if m is 2, 3, 4, or 5 then the substituents R may be the same or different.
3. Compounds according to claim 1, in which X is selected from the group consisting of halogen,, C1-C4-alkyl, C1-C4-halogenoalkyl having l to 5 halogen atoms, C1-C4-alkoxy. n is 1, 2, 3 or 4 and if n is 2, 3, or 4 then the substituents X may be the same or different. R3 and R4 are the same or different and are selected from the group consisting of hydrogen, - COOH, C1-C4-alkyl, C1-C4-halogenoalkyl C1-C4-alkoxy, hydroxy-C1-C4-alkyl, C1-C4-alkoxy-C1- C3-alkyl, C1-C4-alkyl), C1-C4-alkoxycarbonyl, -OC(O)-C1-C4-alkyl, and phenyl. R5 is selected from the group consisting of hydrogen, C3-C6-cycloalkyl, C1-C4-alkylcarbonyl, and C1-C4-alkoxycarbonyl. R is selected from the group consisting of n, nitro, -OH, cyano, C1-C4-alkyl, C1-C4- halogenoalkyl having 1 to 5 halogen atoms, C3-C6-cycloalkyl, C1-C4-alkoxy, C1-C4- alkoxycarbonyl, -NH(C1-C4-alkyl), phenyl (optionally substituted by alkoxy) and phenoxy. m is 0, 1, 2 or3 and if m is 2 or 3 then the substituents R may be the same or different.
4. Compounds according to claim 1, in which R3, R4, R5 represent hydrogen, n represents 2 and X represent 3-Cl and 5-CF3.
5. Compounds according to claim 1, in which R3, R4, R5 represent en, n represents 2 and X represent 3-Cl and 5-Cl.
6. Compounds of formula CF Cl R3 R4 6 N N F F R5 . in which R3, R4 and R5 have the meanings given in claim 1.
7. Compound of formula CF Cl 6 N N F F H .
8. Compounds of formula Cl Cl R3 R4 6 N N F F R5 . in which R3, R4 and R5 have the meanings given in claim 1.
9. Compound of formula Cl Cl 6 N N F F H .
10. Compositions, comprising an ive amount of at least one compound according to claim 1 and at least one tant, solid or liquid diluent.
11. Use of compounds according to claim 1 for controlling plant nematodes.
12. Use of compounds according to claim 1 for the preparation of compositions which can be used as anthelmintic.
13. A compound according to claim 1, substantially as herein described or ified.
14. A compound according to claim 6, substantially as herein described or exemplified.
15. A compound according to claim 7, substantially as herein bed or exemplified.
16. A nd according to claim 8, substantially as herein described or exemplified.
17. A compound according to claim 9, substantially as herein described or exemplified.
18. A composition according to claim 10, substantially as herein described or exemplified.
19. A use according to claim 11, substantially as herein described or exemplified.
20. A use according to claim 12, substantially as herein described or exemplified.
NZ623874A 2011-11-02 2012-10-29 Compounds with nematicidal activity NZ623874B2 (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
EP11187507.6 2011-11-02
EP11187507.6A EP2589292A1 (en) 2011-11-02 2011-11-02 Compounds with nematicidal activity
US201161555127P 2011-11-03 2011-11-03
US61/555,127 2011-11-03
EP11194886.5 2011-12-21
EP11194886.5A EP2606728A1 (en) 2011-12-21 2011-12-21 Compounds with nematicidal activity
PCT/EP2012/071385 WO2013064460A1 (en) 2011-11-02 2012-10-29 Compounds with nematicidal activity

Publications (2)

Publication Number Publication Date
NZ623874A NZ623874A (en) 2016-04-29
NZ623874B2 true NZ623874B2 (en) 2016-08-02

Family

ID=

Similar Documents

Publication Publication Date Title
AU2012331284B2 (en) Compounds with nematicidal activity
ES2280561T3 (en) NEW DERIVATIVES OF PICOLINAMINE AND ITS USE AS FUNGICIDES.
EP2220936B1 (en) Synergistic fungicidal combinations
RU2369095C2 (en) Fungicide composition containing pyridylethylenebenzamide derivative and compound, capable of inhibiting spore germination or growth of micellium through effect on different metabolic routes
US20140256728A1 (en) Compounds with nematicidal activity
WO2015067648A1 (en) Novel compounds for combating arthropods
EP3003042A1 (en) Heterocyclic compounds as pest control agents
BRPI1004930B1 (en) Compounds, fungicidal composition and method for controlling phytopathogenic fungi of crops.
EP2582693A1 (en) Novel ortho-substituted aryl amide derivatives
ES2281536T3 (en) HETEROCICLIC CARBOXAMIDS AND ITS USE AS FUNGICIDES.
BR112012012107B1 (en) Compound, fungicidal composition and method for controlling plant pathogenic fungi
NZ623874B2 (en) Compounds with nematicidal activity
US20160309717A1 (en) Compounds with Nematicidal Activity
EP2443090B1 (en) Substituted enaminocarbonyl compounds for controlling pests
EP2606727A1 (en) Compounds with nematicidal activity
EP2589294A1 (en) Compounds with nematicidal activity
EP2606728A1 (en) Compounds with nematicidal activity
EP2589292A1 (en) Compounds with nematicidal activity