CN1429199A - Insecticidal 1,8-naphthalenedicarboxamides - Google Patents
Insecticidal 1,8-naphthalenedicarboxamides Download PDFInfo
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- CN1429199A CN1429199A CN01805190A CN01805190A CN1429199A CN 1429199 A CN1429199 A CN 1429199A CN 01805190 A CN01805190 A CN 01805190A CN 01805190 A CN01805190 A CN 01805190A CN 1429199 A CN1429199 A CN 1429199A
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- 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
- C07D213/72—Nitrogen atoms
- C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
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- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides
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- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides
- A01N37/24—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides containing at least one oxygen or sulfur atom being directly attached to the same aromatic ring system
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- C07C233/00—Carboxylic acid amides
- C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
- C07C233/66—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups
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- C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
- C07C233/67—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
- C07C233/75—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
- C07C237/28—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton
- C07C237/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton having nitrogen atoms of amino groups bound to the carbon skeleton of the acid part, further acylated
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
- C07C237/48—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring being part of a condensed ring system of the same carbon skeleton
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
- C07C255/42—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms
- C07C255/44—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms at least one of the singly-bound nitrogen atoms being acylated
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- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/58—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton
- C07C255/60—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton at least one of the singly-bound nitrogen atoms being acylated
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- C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/39—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton at least one of the nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom
- C07C323/40—Y being a hydrogen or a carbon atom
- C07C323/42—Y being a carbon atom of a six-membered aromatic ring
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- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
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- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
- C07D231/38—Nitrogen atoms
- C07D231/40—Acylated on said nitrogen atom
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- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
- C07D233/30—Oxygen or sulfur atoms
- C07D233/32—One oxygen atom
- C07D233/38—One oxygen atom with acyl radicals or hetero atoms directly attached to ring nitrogen atoms
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- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members 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
- C07D233/90—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
- C07D295/135—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
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Abstract
Compounds of Formula I and Formula II, and their N-oxides and agriculturally suitable salts, are disclosed that are useful for controlling invertebrate pests, Formula (I), Formula (II) wherein A, B, J, R1, R2, R3, R4, and n are as defined in the disclosure. Also disclosed are compositions comprising the compounds of Formula I or Formula II and methods for controlling invertebrate pests that involve contacting the invertebrate pests or their environment with an effective amount of a compound of Formula (I) or Formula (II).
Description
Background of invention
The present invention relates to specificly 1,8-aphthalimide, its agricultural are suitable for salt and composition, with and in agronomy and non-agronomy environment the using method on the control invertebrate pests.
In order to obtain the high yield of crop, the control invertebrate pests is extremely important.The harm that invertebrate pests causes for the farm crop that grow and store can make output significantly reduce, thereby and causes the human consumer to spend increase.At food and fiber product, livestock, houseware and the aspects such as public and animal health of forestry, chamber crop, ornamental plant, nursery crop, storage, the control invertebrate pests is also very important.Existing many commerical prods are used for these purposes, the new compound that still still constantly needs are more effective, more cheap, toxicity is low, do not harm environment or have the different administration pattern.
EP919542 discloses the phthalic diamide as the formula i of sterilant
Wherein, except that other, Z
1And Z
2Be O and S; And R
1, R
2And R
3Particularly H, alkyl or substituted alkyl.
Summary of the invention
The present invention relates to the compound of formula I and formula II, comprise its all how much and the applicable salt of stereoisomer, N-oxide and agricultural:Wherein each J is benzyl ring, naphthyl member ring systems, 5 or 6 yuan of hetero-aromatic rings or fragrant 8,9 or 10 yuan of assorted dicyclo condensed ring systems independently, and wherein, each ring or member ring systems are randomly with 1-5 R5Replace; A and B are O or S independently; N is 0-4; R1H; Or C1-C
6Alkyl, C2-C
6Alkenyl, C2-C
6Alkynyl or C3-C
6Cycloalkyl is randomly one or more following substituting group replacements that are selected from: halogen, CN, NO separately2, hydroxyl, C1-C
4Alkoxyl, C1-C
4Alkylthio, C1-C
4Alkyl sulfinyl, C1-C
4Alkyl sulphonyl, C2-C
4Alkoxy carbonyl, C1-C
4Alkyl amino, C2-C
8Dialkyl amido and C3-C
6Cycloalkyl amino; Perhaps R1C2-C
6Alkyl-carbonyl, C2-C
6Alkoxy carbonyl, C2-C
6Alkyl amino-carbonyl or C3-C
8Dialkyl amino carbonyl; R2H, C1-C
6Alkyl, C2-C
6Alkenyl, C2-C
6Alkynyl, C3-C
6Cycloalkyl, C1-C
4Alkoxyl, C1-C
4Alkyl amino, C2-C
8Dialkyl amido, C3-C
6Cycloalkyl amino, C2-
C
6Alkoxy carbonyl or C2-C
6Alkyl-carbonyl; R3H; Or C1-C
6Alkyl, C2-C
6Alkenyl, C2-C
6Alkynyl or C3-C
6Cycloalkyl is randomly one or more following substituting group replacements that are selected from: halogen, CN, NO separately2, hydroxyl, C1-C
4Alkoxyl, C1-C
4Alkylthio, C1-C
4Alkyl sulfinyl and C1-C
4Alkyl sulphonyl; Perhaps R2And R3Can form ring by the nitrogen that is connected with them, this ring contains 2-6 carbon atom and randomly contains other nitrogen, sulphur or an oxygen atom together, and this ring optionally is selected from C1-C
2Alkyl, halogen, CN, NO2And C1-C
2The 1-4 of alkoxyl substituting group replaces; With each R4With each R5H, C independently1-C
6Alkyl, C2-C
6Alkenyl, C2-C
6Alkynyl, C3-C
6Cycloalkyl, C1-C
6Haloalkyl, C2-C
6Halogenated alkenyl, C2-C
6Halo alkynyl, C3
-C
6Halogenated cycloalkyl, halogen, CN, CO2H、CONH
2、NO
2, hydroxyl, C1-C
4Alkoxyl, C1-C
4Halogenated alkoxy, C1-C
4Alkylthio, C1-C
4Alkyl sulfinyl, C1-C
4Alkyl sulphonyl, C1-C
4Haloalkyl thio, C1-C
4Haloalkyl sulfinyl, C1-C
4Halogenated alkyl sulfonyl, C2-C
4Alkoxy carbonyl, C1-C
4Alkyl amino, C2-C
8Dialkyl amido, C3
-C
6Cycloalkyl amino, C2-C
6Alkyl-carbonyl, C2-C
6Alkoxy carbonyl, C2-C
6Alkyl amino-carbonyl, C3-C
8Dialkyl amino carbonyl or C3-C
6Trialkylsilkl; Perhaps each R4With each R5Be phenyl, benzyl, phenoxy group, 5 or 6 yuan of hetero-aromatic rings or fragrant 8,9 or 10 yuan of assorted dicyclo condensed ring systems independently, each ring is randomly 1 or 3 and is independently selected from following substituting group replacement: C1-C
4Alkyl, C2-C
4Alkenyl, C2-C
4Alkynyl, C3-C
6Cycloalkyl, C1-C
4Haloalkyl, C2-C
4Halogenated alkenyl, C2-C
4Halo alkynyl, C3-C
6Halogenated cycloalkyl, halogen, CN, NO2、C
1-C
4Alkoxyl, C1-C
4Halogenated alkoxy, C1-C
4Alkylthio, C1-C
4Alkyl sulfinyl, C1-C
4Alkyl sulphonyl, C1-C
4Alkyl amino, C2-
C
8Dialkyl amido, C3-C
6Cycloalkyl amino, C3-C
6(alkyl) cycloalkyl amino, C2-C
4Alkyl-carbonyl, C2-C
6Alkoxy carbonyl, C2-C
6Alkyl amino-carbonyl, C3-C
8Dialkyl amino carbonyl or C3-C
6Trialkylsilkl; Perhaps (R5)
2When be connected in adjacent carbons former gave when upper being combined become-OCF2O-、-CF
2CF
2O-or-OCF2CF
2O-。
The invention still further relates to the composition that is used to control invertebrate pests, comprise formula I or the formula II compound and at least a annexing ingredient that is selected from tensio-active agent, solid diluent and liquid diluent of biologic effective dose.The invention still further relates to a kind of composition, it comprises the formula I of biologic effective dose or at least a additional bioactive compounds or the reagent of formula II compound and significant quantity.
The invention still further relates to the method for control invertebrate pests, comprise invertebrate pests or its environment are contacted with the formula I or the formula II compound (for example as composition described here) of biologic effective dose.The invention still further relates to such method, wherein, invertebrate pests or its environment are contacted with formula I that is used to control invertebrate pests, contain biologic effective dose or formula II compound compositions, or contact with at least a additional compound that contains formula I or formula II compound and biologic effective dose or combination of agents thing, with the control invertebrate pests.
Detailed Description Of The Invention
Hereinbefore, the term " alkyl " that uses separately or use in such as " alkylthio " or compound words such as " haloalkyls " comprises the straight or branched alkyl, as methyl, ethyl, n-propyl, sec.-propyl, or different butyl, amyl group or hexyl isomer." alkenyl " comprises straight or branched alkene class, as 1-propenyl, 2-propenyl, and the different isomerization body of butenyl, pentenyl and hexenyl." alkenyl " also comprises the polyenoid class, as 1, and 2-propadiene and 2,4-hexadiene." alkynyl " comprises straight or branched alkynes class, as 1-proyl, 2-propynyl, and the different isomerization body of butynyl, pentynyl and hexin base." alkynyl " also can comprise the part of being made up of multiple triple bond, as 2, and the 5-hexadiyne." alkoxyl group " comprises for example different isomerization body of methoxyl group, oxyethyl group, positive propoxy, isopropoxy and butoxy, pentyloxy and hexyloxy." alkylthio " comprises branched-chain or straight-chain alkyl sulfo-part, as the different isomerization body of methyl sulfo-, ethylenebis dithiocarbamate and propyl dithiocarbamate, butyl sulfo-, amyl group sulfo-and hexyl sulfo-." cycloalkyl " comprises for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.The definition of " alkylamino ", " alkenyl sulfo-", " alkenyl sulfinyl ", " alkenyl alkylsulfonyl ", " alkynyl sulfo-", " alkynyl sulfinyl ", " alkynyl alkylsulfonyl " or the like is similar to above example.The example of " alkoxy carbonyl " comprises CH
3OC (=O), CH
3CH
2OC (=O), CH
3CH
2CH
2OC (=O), (CH
3)
2CHOC (=O), and the different isomerization body of butoxy carboxyl or pentyloxy carboxyl.The example of " alkylamino carboxyl " comprises CH
3NHC (=O), CH
3CH
2NHC (=O), CH
3CH
2CH
2NHC (=O), (CH
3)
2CHNHC (=O), and the different isomerization body of amino carboxyl of butyl or the amino carboxyl of amyl group.Term " dialkyl amido " comprises the amido functional group of using two alkyl groups replacements that can be identical or different." dialkyl amido carboxyl " definition is similar, and its example comprises (CH
3)
2NC (=O) and CH
3CH
2NCH
3C (=O).
Term " heterocycle " or " heterocyclic system " expression at least one annular atoms wherein are not carbon and comprise 1-4 heteroatomic ring or member ring systems, described heteroatoms is independently selected from nitrogen, oxygen or sulphur, prerequisite is that each heterocycle contains no more than 4 nitrogen, no more than 2 oxygen and no more than 2 sulphur.Can be by any available carbon or nitrogen, be connected with heterocycle by replacing the hydrogen on this carbon or the nitrogen.Term " aromatic ring system " complete unsaturated carbocyclic ring of expression and heterocycle, wherein the polycyclic ring system is aromatics (wherein aromatics represents that described member ring systems satisfies Huckel's rule).The ring of the complete aromaticity of term " hetero-aromatic ring " expression tool, wherein at least one annular atoms is not carbon and comprises 1-4 heteroatoms, described heteroatoms is independently selected from nitrogen, oxygen or sulphur, prerequisite is that each heterocycle contains no more than 4 nitrogen, no more than 2 oxygen and no more than 2 sulphur (wherein the described member ring systems of fragrance expression satisfies Huckel's rule).Can be by any available carbon or nitrogen, be connected with described heterocycle by replacing the hydrogen on this carbon or the nitrogen.Term " aromatic heterocycle system " comprises that at least one ring that complete aromatic heterocycle and polycyclic ring system wherein obtain is fragrant (wherein the described member ring systems of fragrance expression satisfies Huckel's rule) heterocycle.Term " assorted dicyclo condensed ring system " comprises the member ring systems of being made up of two condensed ring, and wherein, at least one annular atoms is not a carbon, and is (as defined above) fragrance or non-fragrance.
Independent or comprising fluorine, chlorine, bromine or iodine such as the term " halogen " in the compound words such as " haloalkyls ".In addition, when being used for such as compound words such as " haloalkyls ", described alkyl can partly or entirely replace with identical or different halogen atom.The example of " haloalkyl " comprises F
3C, ClCH
2, CF
3CH
2And CF
3CCl
2The definition and the term " haloalkyl " of term " halogenated alkenyl ", " halo alkynyl ", " halogenated alkoxy " etc. are similar.The example of " halogenated alkenyl " comprises (Cl
2) C=CHCH
2And CF
3CH
2CH=CHCH
2The example of " halo alkynyl " comprises HC ≡ CCHCl, CF
3C ≡ C, CCl
3C ≡ C and FCH
2C ≡ CCH
2The example of " halogenated alkoxy " comprises CF
3O, CCl
3CH
2O, HCF
2CH
2CH
2O and CF
3CH
2O.
The total number of carbon atoms in the substituted radical is by " C
i-C
j" prefix designates, wherein, i and j are the number of 1-6.For example, C
1-C
3Alkyl sulfonyl basis representation methyl sulphonyl is until the sulfonyl propyl base; C
2Alkoxyalkyl is represented CH
3OCH
2C
3Alkoxyalkyl is represented for example CH
3CH (OCH
3), CH
3OCH
2CH
2Or CH
3CH
2OCH
2And C
4Alkoxyalkyl is represented to contain 4 carbon atoms altogether with the various isomer of the alkyl group of alkoxy base replacement, and example comprises CH
3CH
2CH
2OCH
2And CH
3CH
2OCH
2CH
2In the middle of cited in the above, when the compound of formula 1 contained heterocycle, all substituting groups were all by any available carbon or nitrogen, be connected with this ring by replacing the hydrogen on this carbon or the nitrogen.
When group contains the substituting group that can be hydrogen, R for example
3, then when this substituting group is hydrogen, think that promptly being equivalent to this group is not substituted.Take up an official post when selecting substituent number to be 0 when group, for example when n is 0, think that then being equivalent to this group is not substituted.When key is denoted as when not fixing, then substituting group can be by the replacement of hydrogen be connected with any available carbon atom on the ring; For bicyclic system, one or more substituting groups can be connected with any ring in the bicyclic system, or all are connected with two rings.For example when n is 1, single R
4Substituting group can be on 2,3,4,5,6 or 7 indicated any position connection mode I or formula II; And when n is 2,2 R independently
4Substituting group can be 2,3; 2,4; 2,5; 2,6 or 2,7 or connection in any other combination of two.Work as R
2And R
3The nitrogen that is connected with them closes when forming ring, and then this ring can any therein available carbon or randomly randomly replaced on any available nitrogen.
Compound of the present invention can be used as one or more steric isomers and exists.Described various steric isomer comprises enantiomer, diastereomer, atropisomer and geometrical isomer.It will be appreciated by those skilled in the art that when a kind of isomer is enrichment with respect to other isomer or when with other isomer separation, it can be more active and/or can has advantageous effect.In addition, how to those skilled in the art will know that to described isomer separate, enrichment and/or selectivity preparation.Compound of the present invention can exist with isomer mixture, individual isomer or with the optically-active form body.
The compound that the present invention includes is selected from formula I or formula II, its N-oxide compound and agricultural are suitable for salt.It will be appreciated by those skilled in the art that not all nitrogen heterocyclic ring can form the N-oxide compound, this is because nitrogen needs utilizable lone-pair electron to be oxidized to oxide compound; Those skilled in the art should be able to discern those nitrogen heterocyclic rings that can form the N-oxide compound.Those skilled in the art will be appreciated that also tertiary amine can form the N-oxide compound.The synthetic method of the oxynitride of preparation heterocycle and tertiary amine is well known to those skilled in the art, and comprises with peroxy acid (as peracetic acid and metachloroperbenzoic acid (MCPBA)), hydrogen peroxide, alkyl peroxide (as t-butyl hydroperoxide), Sodium peroxoborate and bisoxirane class (as dimethyldioxirane) heterocycle and tertiary amine are carried out oxygenizement.These preparation methods to the N-oxide compound have done extensive description and comment in the literature, referring to for example: T.L.Gilchrist is at Comprehensive Organic Synthesis (comprehensive organic synthesis) the 7th volume 748-750 page or leaf, S.V.Ley edits, Pergamon press; M.Tisler and B.Stanovnik are at Comprehensive Heterocyclic Chemistry (comprehensive heterocyclic chemistry) the 3rd volume 18-19 page or leaf, and A.J.Boulton and A.McKillop edit, Pergamon press; M.R.Grimmett and B.R.T.Keene are at Advances inHeterocyclic Chemistry (heterocyclic chemistry progress) the 43rd volume 139-151 page or leaf, and A.R.Katritzky edits, Academic press; M.Tisler and B.Stanovnik are at Advancesin Heterocyclic Chemistry the 9th volume 285-291 page or leaf, and A.R.Katritzky and A.J.Boulton edit, Academic press; And G.W.H.Cheeseman and E.S.G.Werstiuk be at Advances in Heterocyclic Chemistry the 22nd volume 390-392 page or leaf, and A.R.Katritzky and A.J.Boulton edit, Academic press.
The salt of The compounds of this invention comprise with such as the inorganic or organic acid acid salt of Hydrogen bromide, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, fumaric acid, lactic acid, toxilic acid, propanedioic acid, oxalic acid, propionic acid, Whitfield's ointment, tartrate, 4-toluenesulphonic acids or valeric acid.
Make synthetic carrying out easily and/or cause that higher arthropod insect sandworm is renderd a service in order to comprise, preferably: preferred 1. formula I compounds, wherein
A and B are 0; R
1Be H, C
1-C
4Alkyl, C
2-C
4Alkenyl, C
2-C
4Alkynyl, C
3-C
6Cycloalkyl, C
2-C
6Alkyl-carbonyl or C
2-C
6Alkoxy carbonyl; With n be 0-2.Preferred 2. formula II compounds, wherein
A and B are 0; R
1Be H, C
1-C
4Alkyl, C
2-C
4Alkenyl, C
2-C
4Alkynyl, C
3-C
6Cycloalkyl, C
2-C
6Alkyl-carbonyl or C
2-C
6Alkoxy carbonyl; With n be 0-2.Preferred 3. preferred 1 or preferred 2 compound, wherein J is benzyl ring or 5 yuan or 6 yuan of hetero-aromatic rings that are selected from following J-1, J-2, J-3 and J-4, every-J ring is randomly used 1-3 R
5Replace
Q is O, S or NR
5W, X, Y and Z are N or CR independently
5, prerequisite is that W, X, Y or Z are N one of at least in J-3 and J-4; R
2Be H, C
1-C
4Alkyl, C
2-C
4Alkenyl, C
2-C
4Alkynyl, C
3-C
6Cycloalkyl, C
2-C
6Alkyl-carbonyl or C
2-C
6Alkoxy carbonyl; R
3Be C
1-C
6Alkyl, C
2-C
6Alkenyl, C
2-C
6Alkynyl or C
3-C
6Cycloalkyl randomly is one or more following substituting group replacements that are selected from: halogen, CN, C separately
1-C
2Alkoxyl group, C
1-C
2Alkylthio, C
1-C
2Alkyl sulfinyl and C
1-C
2Alkyl sulphonyl; A R
4Group connects the naphthyl member ring systems at 2 or 7, and this R
4Be C
1-C
4Alkyl, C
1-C
4Haloalkyl, halogen, CN, NO
2, C
1-C
4Alkoxyl group, C
1-C
4Halogenated alkoxy, C
1-C
4Alkylthio, C
1-C
4Alkyl sulfinyl, C
1-C
4Alkyl sulphonyl, C
1-C
4Haloalkyl thio, C
1-C
4Haloalkyl sulfinyl or C
1-C
4Halogenated alkyl sulfonyl; Each R
5Be H, C independently
1-C
4Alkyl, C
1-C
4Haloalkyl, halogen, CN, NO
2, C
1-C
4Alkoxyl group, C
1-C
4Halogenated alkoxy, C
1-C
4Alkylthio, C
1-C
4Alkyl sulfinyl, C
1-C
4Alkyl sulphonyl, C
1-C
4Haloalkyl thio, C
1-C
4Haloalkyl sulfinyl, C
1-C
4Halogenated alkyl sulfonyl or C
2-C
4Alkoxy carbonyl, C
3-C
8Dialkyl amino carbonyl; Or each R
5Be phenyl, benzyl or 5 yuan or 6 yuan of hetero-aromatic rings independently, each ring randomly is that following substituting group replaces: C
1-C
4Alkyl, C
2-C
4Alkenyl, C
2-C
4Alkynyl, C
3-C
6Cycloalkyl, C
1-C
4Haloalkyl, C
2-C
4Halogenated alkenyl, C
2-C
4Halo alkynyl, C
3-C
6Halogenated cycloalkyl, halogen, CN, NO
2, C
1-C
4Alkoxyl group, C
1-C
4Halogenated alkoxy, C
1-C
4Alkylthio, C
1-C
4Alkyl sulfinyl, C
1-C
4Alkyl sulphonyl, C
1-C
4Alkylamino, C
2-C
8Dialkyl amido, C
3-C
6Cycloalkyl amino, C
3-C
6(alkyl) cycloalkyl amino, C
2-C
4Alkyl-carbonyl, C
2-C
6Alkoxy carbonyl, C
2-C
6Alkyl amino-carbonyl, C
3-C
8Dialkyl amino carbonyl or C
3-C
6Trialkylsilkl; Or (R
5)
2Can lump together when being connected with adjacent carbons becomes-OCF
2O-,-CF
2CF
2O-or-OCF
2CF
2O-; With n be 1-2.Preferred 4. preferred 3 formula I compound, wherein R
2Be H; R
3Be C
1-C
4Alkyl; With at least one R
5Substituting group and NR
1C (=B) part ortho position.Preferred 5. preferred 4 compound, wherein R
3It is methyl.Preferred 6. preferred 3 formula II compound, wherein
R
1Be H or C
1-C
4Alkyl;
R
2Be H or C
1-C
4Alkyl;
R
3Be randomly to use halogen, CN, OCH
3Or S (O)
pCH
3The C that replaces
1-C
4Alkyl; A R
5Group with C (=B) NR
1The part adjacent links to each other with J on the position, and this R
5Be C
1-C
4Alkyl, C
1-C
4Haloalkyl, halogen, CN, NO
2, C
1-C
4Alkoxyl group, C
1-C
4Halogenated alkoxy, C
1-C
4Alkylthio, C
1-C
4Alkyl sulfinyl, C
1-C
4Alkyl sulphonyl, C
1-C
4Haloalkyl thio, C
1-C
4Haloalkyl sulfinyl, C
1-C
4Halogenated alkyl sulfonyl or C
2-C
4Alkoxy carbonyl; C
3-C
8Dialkyl amino carbonyl or phenyl, benzyl, or 5 yuan or 6 yuan of hetero-aromatic rings, each ring randomly are that following substituting group replaces: halogen, CN, NO
2, C
1-C
4Alkyl, C
2-C
4Alkenyl, C
2-C
4Alkynyl, C
3-C
6Cycloalkyl, C
1-C
4Haloalkyl, C
1-C
4Alkoxyl group or C
1-C
4Halogenated alkoxy; And the 2nd optional R
5Group is C independently
1-C
4Alkyl, C
1-C
4Haloalkyl, halogen, CN, NO
2, C
1-C
4Alkoxyl group, C
1-C
4Halogenated alkoxy, C
1-C
4Alkylthio, C
1-C
4Alkyl sulfinyl, C
1-C
4Alkyl sulphonyl, C
1-C
4Haloalkyl thio, C
1-C
4Haloalkyl sulfinyl, C
1-C
4Halogenated alkyl sulfonyl or C
2-C
4Alkoxy carbonyl; C
3-C
8Dialkyl amino carbonyl or phenyl, benzyl, or 5 yuan or 6 yuan of hetero-aromatic rings, each ring randomly are that following substituting group replaces: halogen, CN, NO
2, C
1-C
4Alkyl, C
2-C
4Alkenyl, C
2-C
4Alkynyl, C
3-C
6Cycloalkyl, C
1-C
4Haloalkyl, C
1-C
4Alkoxyl group or C
1-C
4Halogenated alkoxy.Preferred 7. preferred 6 compound, wherein J is phenyl, pyrazoles, pyrroles, pyridine or pyrimidine, each all by with C (=B) NR
1A R5 and second optional R of linking to each other with J on the part adjacent position
5Replace.Preferred 8. preferred 7 compound, wherein R
1And R
2All are H; A R
4With NR
1C (=X) 7 of J part adjacent are gone up and are connected, and be selected from C
1-C
3Alkyl, CF
3, OCF
3, OCHF
2, S (O)
pCF
3, S (O)
pCHF
2And halogen, and the 2nd optional R
4With NR
1C (=X) 5 upward connections of J part contraposition, and be selected from halogen, C
1-C
3Alkyl and C
1-C
3Haloalkyl.Preferred 9. preferred 8 compound, wherein J is J-1; Q is NR
5aX is N or CH; Y is CH; Z is CR
5bR
5aBe to be selected from halogen, C with one or two
1-C
4Alkyl, C
1-C
4Haloalkyl or C
1-C
4Phenyl that halogenated alkoxy replaced or 2-pyridyl; And R
5bBe halogen or CF
3
Particularly preferred compound is selected from N-methyl-N '-(2-bromo-4-fluorophenyl)-1,8-naphthalene-two formyl, N-methyl 8-[(3,4-difluorophenyl) carbonylamino]-1-naphthoyl and N-methyl 8-[(2-thienyl) carbonylamino]-the 1-naphthoyl.
The invention still further relates to a kind of composition of controlling invertebrate, comprise formula I or the formula II compound and at least a component that is selected from tensio-active agent, solid diluent and liquid diluent of biologic effective dose.The invention still further relates to a kind of composition, comprise the formula I of biologic effective dose or at least a additional bioactive compounds or the reagent of formula II compound and significant quantity.Preferred compositions contains preferred formula I or formula II compound and above-mentioned particularly preferred compound among the preferred 1-9.
The invention still further relates to the arthropodan method of control, comprise making arthropods or its environment with effectively the formula I or the suitable salt (for example to contain the form of formula I or formula II compound compositions) of formula II compound, its N-oxide compound or agricultural of amount contact for killing arthropods.The invention still further relates to a kind of like this method, wherein, make the formula I or the formula II compound of invertebrate pests or its environment and biologic effective dose or contain formula I or at least a additional compound of formula II compound and biologic effective dose or combination of agents thing contact, with the control invertebrate pests.Preferable methods comprises preferred formula I or formula II compound and above-mentioned particularly preferred compound among the preferred 1-9.
Importantly some following formula Ih and formula IIc compound comprise geometry and stereoisomer and the applicable salt of agricultural that they are all:Wherein: A and B are O or S independently; M is 1-5; N is 0-4; R1H; Or C1-C
6Alkyl, C2-C
6Alkenyl, C2-C
6Alkynyl or C3-C
6Cycloalkyl is randomly one or more following substituting group replacements that are selected from: halogen, CN, NO separately2, hydroxyl, C1-C
4Alkoxyl, C1-C
4Alkylthio, C1-C
4Alkyl sulfinyl, C1-C
4Alkyl sulphonyl, C2-C
4Alkoxy carbonyl, C1-C
4Alkyl amino, C2-C
8Dialkyl amido and C3-C
6Cycloalkyl amino; Perhaps R1C2-C
6Alkyl-carbonyl, C2-C
6Alkoxy carbonyl, C2-C
6Alkyl amino-carbonyl or C3-C
8Dialkyl amino carbonyl; R2H, C1-C
6Alkyl, C2-C
6Alkenyl, C2-C
6Alkynyl, C3-C
6Cycloalkyl, C1-C
4Alkoxyl, C1-C
4Alkyl amino, C2-C
8Dialkyl amido, C3-C
6Cycloalkyl amino, C2-
C
6Alkoxy carbonyl or C2-C
6Alkyl-carbonyl; R3H; Or C1-C
6Alkyl, C2-C
6Alkenyl, C2-C
6Alkynyl or C3-C
6Cycloalkyl is randomly one or more following substituting group replacements that are selected from: halogen, CN, NO separately2, hydroxyl, C1-C
4Alkoxyl, C1-C
4Alkylthio, C1-C
4Alkyl sulfinyl and C1-C
4Alkyl sulphonyl; Perhaps R2And R3Can form ring by the nitrogen that is connected with them, this ring contains 2-6 carbon atom and randomly contains other nitrogen, sulphur or an oxygen atom together, and this ring optionally is selected from C1-C
2Alkyl, halogen, CN, NO2And C1-C
2The 1-4 of alkoxyl substituting group replaces; With each R4With each R5H, C independently1-C
6Alkyl, C2-C
6Alkenyl, C2-C
6Alkynyl, C3-C
6Cycloalkyl, C1-C
6Haloalkyl, C2-C
6Halogenated alkenyl, C2-C
6Halo alkynyl, C3
-C
6Halogenated cycloalkyl, halogen, CN, CO2H、CONH
2、NO
2, hydroxyl, C1-C
4Alkoxyl, C1-C
4Halogenated alkoxy, C1-C
4Alkylthio, C1-C
4Alkyl sulfinyl, C1-C
4Alkyl sulphonyl, C1-C
4Haloalkyl thio, C1-C
4Haloalkyl sulfinyl, C1-C
4Halogenated alkyl sulfonyl, C2-C
4Alkoxy carbonyl, C1-C
4Alkyl amino, C2-C
8Dialkyl amido, C3
-C
6Cycloalkyl amino, C2-C
6Alkyl-carbonyl, C2-C
6Alkoxy carbonyl, C2-C
6Alkyl amino-carbonyl, C3-C
8Dialkyl amino carbonyl or C3-C
6Trialkylsilkl; Perhaps each R4With each R5The phenyl that randomly for following substituting group, replaces: C independently1-C
4Alkyl, C2-C
4Alkenyl, C2-C
4Alkynyl, C3-C
6Cycloalkyl, C1-C
4Haloalkyl, C2-C
4Halogenated alkenyl, C2-C
4Halo alkynyl, C3-C
6Halogenated cycloalkyl, halogen, CN, NO2、C
1
-C
4Alkoxyl, C1-C
4Halogenated alkoxy, C1-C
4Alkylthio, C1-C
4Alkyl sulfinyl, C1-C
4Alkyl sulphonyl, C1-C
4Alkyl amino, C2-C
8Dialkyl amido, C3-C
6Cycloalkyl amino, C3-C
6(alkyl) cycloalkyl amino, C2-C
4Alkyl-carbonyl, C2-C
6Alkoxy carbonyl, C2-C
6Alkyl amino-carbonyl, C3-C
8Dialkyl amino carbonyl or C3-C
6Trialkylsilkl.
It is also important that the composition of killing the segmental appendage insect, comprise for killing segmental appendage insect effectively above-mentioned formula Ih or the formula IIc compound and at least a component that is selected from tensio-active agent, solid diluent or liquid diluent of amount.
The invention still further relates to the arthropodan method of control, comprise making arthropods or its environment with effectively the above-mentioned formula Ih or the formula IIc compound of amount contact for killing arthropods.
Part 1. is the compound through selecting of formula Ih importantly, wherein
A and B are 0;
M is 1-3;
N is 0-2; R
1Be H, C
1-C
4Alkyl, C
2-C
4Alkenyl, C
2-C
4Alkynyl, C
3-C
6Cycloalkyl, C
2-C
6Alkyl-carbonyl or C
2-C
6Alkoxy carbonyl; With each R
4With each R
5Be H, C independently
1-C
4Alkyl, C
1-C
4Haloalkyl, C
1-C
4Halogenated alkoxy, C
1-C
4Alkylthio, C
1-C
4Alkyl sulfinyl, C
1-C
4Alkyl sulphonyl, C
1-C
4Haloalkyl thio, C
1-C
4Haloalkyl sulfinyl, C
1-C
4Halogenated alkyl sulfonyl or C
2-C
4Alkoxy carbonyl.
Part 2. is the compound through selecting of part 1 importantly, wherein
R
2Be H;
R
3Be C
1-C
4Alkyl; Each R
4With each R
5Be H, C independently
1-C
4Alkyl, C
1-C
4Haloalkyl, halogen, CN, NO
2, C
1-C
4Alkoxyl group, C
1-C
4Halogenated alkoxy, C
1-C
4Alkylthio, C
1-C
4Alkyl sulfinyl, C
1-C
4Alkyl sulphonyl, C
1-C
4Haloalkyl thio, C
1-C
4Haloalkyl sulfinyl, C
1-C
4Halogenated alkyl sulfonyl or C
2-C
4Alkoxy carbonyl; With at least one R
5Substituting group is the ortho position at amido linkage; Part 3. is the compound through selecting of part 2 importantly, wherein R
3It is methyl.Part 4. is the compound through selecting of formula IIc importantly, wherein
A and B all not 0;
M is 1-3;
N is 0-2; R
1Be H, C
1-C
4Alkyl, C
2-C
4Alkenyl, C
2-C
4Alkynyl, C
3-C
6Cycloalkyl, C
2-C
6Alkyl-carbonyl or C
2-C
6Alkoxy carbonyl; With each R
4With each R
5Be H, C independently
1-C
4Alkyl, C
1-C
4Haloalkyl, halogen, CN, NO
2, C
1-C
4Alkoxyl group, C
1-C
4Halogenated alkoxy, C
1-C
4Alkylthio, C
1-C
4Alkyl sulfinyl, C
1-C
4Alkyl sulphonyl, C
1-C
4Haloalkyl thio, C
1-C
4Haloalkyl sulfinyl, C
1-C
4Halogenated alkyl sulfonyl or C
2-C
4Alkoxy carbonyl.Part 5. is the compound through selecting of part 4 importantly, wherein
R
2Be H;
R
6Be randomly to be C
1-C
4Alkoxyl group or C
1-C
4The C that alkylthio replaces
1-C
6Alkyl; Each R
4With each R
5Be H, C independently
1-C
4Alkyl, C
1-C
4Haloalkyl, halogen, CN, NO
2, C
1-C
4Alkoxyl group, C
1-C
4Halogenated alkoxy, C
1-C
4Alkylthio, C
1-C
4Alkyl sulfinyl, C
1-C
4Alkyl sulphonyl, C
1-C
4Haloalkyl thio, C
1-C
4Haloalkyl sulfinyl, C
1-C
4Halogenated alkyl sulfonyl or C
2-C
4Alkoxy carbonyl; With at least one R
5Substituting group is the ortho position at amido linkage.
As noted above, each J is benzyl ring, naphthyl member ring systems, 5 or 6 yuan of hetero-aromatic rings or fragrant 8,9 or 10 yuan of assorted dicyclo condensed ring systems independently, and wherein, each ring or member ring systems randomly are to replace with 1-5 R5.The term that is associated with these J groups " randomly replacement " is meant unsubstituted group or has at least one non-hydrogen substituting group that its activity of killing the segmental appendage insect that does not make unsubstituted analogue and had disappears.Randomly use 1-5 R
5The example of the phenyl that replaces is the ring of representing with U-1 in display 1, wherein R
vBe R
5, and r is the integer of 1-5.Randomly use 1-5 R
5The example of the naphthyl that replaces is the ring of representing with U-85 in display 1, wherein R
vBe R
5, and r is the integer of 1-5.Randomly use 1-5 R
5The example of 5 yuan or 6 yuan hetero-aromatic rings that replace is included in the ring that U-2 to U-53 represents in the display 1, wherein R
vBe R
5, and r is the integer of 1-5.Notice that following J-1 to J-4 also represents 5 yuan or 6 yuan of hetero-aromatic rings.Notice that U-2 to U-20 is the example of J-1, U-21 to U-35 and U-40 are the examples of J-2, and U-41 to U-48 is the example of J-3, and U-49 to U-53 is the example of J-4.Randomly with 1-4 R
3The example of 8, the 9 or 10 yuan of assorted dicyclo condensed ring systems of fragrance that replace comprises illustrated U-54 to U-84, wherein R in the display 1
vBe R
5, and r is the integer of 1-5.
Although R
vGroup appears in the structure of U-1 to U-85, but it should be noted that they are not to exist, and this is because they are substituting groups of choosing wantonly.It should be noted R when linking to each other with atom
vWhen being H, it is equal to as this atom and is not substituted.Need fill its valent nitrogen-atoms with H or R by replacing
vReplace.It should be noted that some U groups can only be with the R that is less than 5
vGroup replaces that (for example U-14, U-15, U-18 to U-21 and U-32 to U-34 can only be with R
vReplace).It should be noted, as (R
v)
rAnd the tie point between the U group is represented as when not fixing (R
v)
rCan be connected with any operable carbon atom on the U group.It should be noted that when the tie point on the U group is represented as when not fixing, the U group can be connected by any operational carbon on the U group with the rest part of formula I by replacing hydrogen atom.
Display 1
The compound of formula I and formula II can be by being prepared as described following one or more methods of reaction scheme 1-21 or variation.At the R described in the following reaction scheme
1, R
2, R
3, R
4, A, B, m and n definition such as in foregoing invention general introduction or its accessory constituent definition.
The compound of formula I can be prepared by the program that reaction scheme 1-9 is summarized.The compound of formula Ia-h is each subset of formula I compound.
Exemplary program is described in the reaction scheme 1, and relates at alkali and existing or being connected of the amine of the different naphthyl methylene imide (isonaphthalimide) of non-existent situation following formula 2 and formula 3 or being connected of the amine of the compound of formula 4 and formula 5.Typical alkali comprises amine alkali, as triethylamine, diisopropylethylamine and pyridine.In some cases, it is useful using the acid scavenger of polymkeric substance support such as the diisopropylethylamine of polymkeric substance combination and the dimethyl aminopyridine of polymkeric substance combination.The amine of formula 3 and formula 5 be commercially available, in chemical literature, fully describe, or be easy to obtain by the document step of having established.Utilize various standard sulfo-transfer agents to comprise thiophosphoric anhydride and Lawesson reagent, the acid amides of formula Ia can be converted into the thioamides of formula Ib.
Reaction scheme 1
The compound of formula 2 and formula 4 is normally by with 1 of formula 6, and 8-naphthoyl chlorine (1,8-naphthaloyl chloride) is connected with the amine of the amine of formula 7 or formula 8 respectively and (reaction scheme 2) that prepare.Typical acid scavenger comprises amine alkali, as triethylamine, diisopropylethylamine and pyridine.In some cases, it is useful using the acid scavenger of polymkeric substance support such as the diisopropylethylamine of polymkeric substance combination and the dimethyl aminopyridine of polymkeric substance combination.In some cases, the amine of formula 7 can be used as acid scavenger when excessive use.1 of formula 6,8-naphthoyl chlorine compound has carried out abundant description in chemical literature, and normally by corresponding 1,8-naphthalic acid or acid anhydrides, use are generally used for carboxylic acid to the chlorination reagent preparation of the conversion of carboxyl acyl chloride (carboxylic acid chloride).These normally used chlorination reagents comprise phosphorus oxychloride and phosphorus pentachloride.
Reaction scheme 2
The program of selective preparation formula 2 and formula 4 compounds relates separately to the cyclic action (reaction scheme 3) of the 8-aminocarboxyl-1-naphthoic acid of formula 9 and formula 10, it be utilize dehydrated reagent, in inert solvent, in-30 to 30 ℃ the temperature range, acid scavenger exists or non-existent situation under carry out.Typical dehydrated reagent comprises dicyclohexylcarbodiimide and trifluoro-acetic anhydride.The dicyclohexylcarbodiimide of the reagent of polymkeric substance support such as polymkeric substance combination is useful.Typical acid scavenger comprises amine alkali, as triethylamine, diisopropylethylamine and pyridine.In some cases, it is useful using the acid scavenger of polymkeric substance support such as the diisopropylethylamine of polymkeric substance combination and the dimethyl aminopyridine of polymkeric substance combination.Typical inertia reagent comprises aprotic solvent, as methylene dichloride and 1-chlorobutane.The type reaction stable range is-5 to 25 ℃.
Reaction scheme 3
The preparation of the 8-aminocarboxyl-1-naphthoic acid of formula 9 and formula 10 relates in inert solvent, in the temperature range of 0-30 ℃, make 1 of formula 11, and the 8-naphthalic anhydride is connected (reaction scheme 4) with the amine of formula 7 or the amine of formula 8 respectively.Typical inertia reagent is dimethyl formamide.Reaction is normally carried out in 5-10 ℃ stable range.
Reaction scheme 4
The program of the 8-aminocarboxyl-1-naphthoic acid of selective preparation formula 9 and formula 10 relates separately to 1 of formula 12 and formula 13, the imido hydrolysis of 8-naphthyl methylene (reaction scheme 5), this hydrolysis utilizes oxyhydroxide such as sodium hydroxide or potassium hydroxide, in protonic solvent system such as water-methanol or water-dioxan, at high temperature carry out.This reaction is normally carried out under the reflux temperature of reaction mixture.1 of formula 12 and formula 13,8-naphthyl methylene imide compound normally is prepared as follows: promptly usually in the presence of acid, at high temperature make 1 of formula 11, the 8-naphthalic anhydride respectively with the amine condensation of formula 7 or formula 8.Type reaction relates to 1 of the formula 11 that makes, and the amine of 8-naphthalic anhydride and formula 7 or formula 8 refluxes in acetic acid.
Reaction scheme 5
The program of a selective preparation I compound relates to the 8-aminocarboxyl-1-naphthoyl chloride that makes formula 14 and formula 15 in the presence of acid scavenger and is connected (reaction scheme 6) with the amine of formula 3 or the amine of formula 5 respectively.Typical acid scavenger comprises amine alkali, as triethylamine, diisopropylethylamine and pyridine.In some cases, it is useful using the acid scavenger of polymkeric substance support such as the diisopropylethylamine of polymkeric substance combination and the dimethyl aminopyridine of polymkeric substance combination.Usually range of reaction temperature is 0-25 ℃.
By make 1 of corresponding formula 6 in the presence of acid scavenger, 8-naphthoyl dichloro (1, the 8-naphthaloyl dichloride) amine with formula 5 or formula 3 respectively is connected, and can obtain the 8-aminocarboxyl-1-naphthoyl chloride (reaction scheme 7) of formula 14 and formula 15.Typical acid scavenger comprises amine alkali, as triethylamine, diisopropylethylamine and pyridine.In some cases, it is useful using the acid scavenger of polymkeric substance support such as the diisopropylethylamine of polymkeric substance combination and the dimethyl aminopyridine of polymkeric substance combination.
Reaction scheme 6
Reaction scheme 7 Another program of preparation I compound relates to the carbamoylation or the sulfo-carbamoylation (reaction scheme 8 and 9) of proceed step by step of the naphthalene of formula 20.When under the condition of Friedel-Crafts reaction, handling with Lewis acid, the 1-naphthoamide of formula 16 or formula 17 or 1-naphthalene thioformamide (1-naphthalenethiocarboxamide) are connected with the urea chloride or the thiocarbamyl chlorine of formula 18 or formula 19, and the compound (reaction scheme 8) of formula I is provided.Lewis acid commonly used comprises chlorination chlorine and tin chloride.
The preparation of the 1-naphthoamide of formula 16 or formula 17 or 1-naphthalene thioformamide (reaction scheme 9) relates under the condition of Friedel-Crafts reaction, in the presence of Lewis acid such as chlorination chlorine and tin chloride, and the naphthalene of formula 20 is connected with the urea chloride or the thiocarbamyl chlorine of formula 19 or formula 18 respectively.The urea chloride or the thiocarbamyl chlorine of the naphthalene of formula 20, formula 18 and formula 19 are commercially available getting, and fully are described in chemical literature, perhaps abide by the document program of having established and are prepared.
Reaction scheme 8
Reaction scheme 9
The compound of formula II can be by the method described in the following reaction scheme 10-13 or one or more preparations in the change scheme.The compound of formula IIa-b is the subclass of formula II compound.
Exemplary program is described in the reaction scheme 10 and relates to the 8-amino-naphthalene-1-carboxamide that makes formula 21 and is connected with the carbonyl chloride of formula 22 in the presence of acid scavenger, so that the compound of formula IIa to be provided, perhaps in the presence of aromatic hydrocarbons selenol salt (areneselenolate), be connected, so that the compound of formula IIb to be provided with the sulfo-carbonyl chloride of formula 22.Typical acid scavenger comprises amine alkali, and as triethylamine, diisopropylethylamine and pyridine, other acid scavenger comprises oxyhydroxide such as sodium hydroxide and potassium hydroxide, and carbonate such as yellow soda ash and salt of wormwood.In some cases, it is useful using the acid scavenger of polymkeric substance support such as the diisopropylethylamine of polymkeric substance combination and the dimethyl aminopyridine of polymkeric substance combination.Typical aromatic hydrocarbons selenol salt comprises aromatic hydrocarbons selenol sodium.The carbonyl chloride of formula 22 and sulfo-carbonyl chloride are commercially available getting, and fully are described in chemical literature, perhaps abide by the document program of having established and are easy to be prepared.Utilize standard sulfo-transfer agent such as thiophosphoric anhydride and Lawesson reagent the acid amides of formula IIa can be converted into the thioamides of IIb.
Reaction scheme 10
Another program of preparation formula IIa compound relates to the 1-amino-naphthalene-8-carboxamide or the 1-amino-naphthalene-8-thiocarbamoyl that make formula 21 in the presence of dehydrated reagent such as dicyclohexylcarbodiimide (DCC) and is connected with the carboxylic acid of formula 23.The dicyclohexylcarbodiimide of the reagent of polymkeric substance support such as polymkeric substance combination is useful.The phenylformic acid of formula 23 is commercially available getting, and fully is described in chemical literature, perhaps abides by the document program of having established and is easy to be prepared.Because it is very extensive to be used to prepare the document of carboxamide, so the program of reaction scheme 10 and reaction scheme 11 only is the representative example of the process useful of preparation formula II compound.
Reaction scheme 11
8-amino-naphthalene of formula 21a-1-carboxamide or 8-amino-naphthalene-1-thiocarbamoyl is normally obtained by the corresponding 8-nitro-naphthalene-1-carboxamide and the 8-nitro-naphthalene-1-thiocarbamoyl of formula 24 respectively by the reduction nitryl group.Exemplary program relates to the reductive action of carrying out with hydrogen in the presence of metal catalyst on carbon or the platinum oxide such as the palladium, in hydroxylic solvent such as ethanol and Virahol.These methods have been done abundant record in chemical literature.By known method, comprise direct alkylation or, can introduce R in this stage usually by the common preferably reductive alkylation of amine
1Substituting group such as alkyl, substituted alkyl etc.Normally used method is in the presence of reductive agent such as cyano group sodium borohydride, amino naphthalenes 21a is combined, with the compound of production 21, wherein R with aldehyde
1Not H.
Reaction scheme 12
Be easy to the middle acid amides of preparation formula 24 by 8-nitro-naphthalene-1-formic acid, 8-nitro-naphthalene-1-formic acid is known in commercially available, the document, or prepares by the derivatization of establishing in the literature, be used for naphthalene or be common to the virtue group.The typical method that forms acid amides can use at this.These dehydrations that comprise that the amine of the acid of formula 25 and formula 5 utilizes DCC for example to carry out are connected, and make acid be converted into activity form such as chloride of acid or acid anhydrides, are connected with amine subsequently, form the acid amides of formula 24a.In addition, diethyl phosphorocyanidate is to be used for the useful reagent that this class relates to the acid activation effect.For this class reaction, chemical literature is very abundant.Utilize commercially available sulfo-transfer agent such as thiophosphoric anhydride and Lawesson reagent, the acid amides of formula 24a is easy to be converted into the thioamides of formula 24b.
Reaction scheme 13
The phenylformic acid of formula 23a (compound of formula 23, the wherein randomly substituted benzyl ring of J) is well-known in the art.The preparation of some heterocyclic acids of formula 4 is described among the reaction scheme 14-21.Various heterocyclic acids and common synthetic method thereof are found among the WO 98/57397.
Reaction scheme 14 has been described the synthetic of representative pyridine acid (23b).Described method relates to known by beta-ketoester and 4-aminobutene ketone (29) pyridine synthesis.Substituent R
5(c) and R
5(d) comprise for example alkyl and haloalkyl.
Reaction scheme 14
Reaction scheme 15 has been described the synthetic of representative pyrimidine acid (23c).Described method relates to known by vinylidene-beta-ketoester (33) and the synthetic pyrimidine of amidine (34).Substituent R
5(c) and R
5(d) comprise for example alkyl and haloalkyl.
Reaction scheme 15
Reaction scheme 16-21 has described the synthetic of representative pyrazoles acid (23d).The synthetic committed step of 23d relates to arylation or the alkylation introducing R by pyrazoles in the reaction scheme 16
5(c) substituting group.Arylating agent or alkylating agent R
5(c)-and Lg (wherein Lg is a leavings group, as Cl, Br, I, and sulfonate radical such as tosic acid root or methanesulfonate, or sulfate radical is as-SO
2OR
5(c)) comprise R
5(c) group is as C
1-C
6Alkyl, C
2-C
6Alkenyl, C
2-C
6Alkynyl, C
2-C
6Alkyl-carbonyl, C
2-C
6Alkoxy carbonyl, C
3-C
8Dialkyl amino carbonyl, C
3-C
6Trialkylsilkl; Or phenyl, benzyl, benzoyl, each ring or member ring systems 5 yuan or 6 yuan of hetero-aromatic rings randomly being replaced.The oxygenizement of methyl group produces pyrazole carboxylic acid.Some preferred R
5(d) group comprises alkylthio.
Reaction scheme 16
Reaction scheme 17 has been described pyrazoles synthetic of formula 23d.These acid can followingly be synthesized: make the compound metalization of formula 40 by utilizing LDA (LDA), then by make the lithium salts quenching with carbonic acid gas, produced the metalation of utilizing LDA (LDA), the carboxylation of formula 40 compounds is committed steps.R
5(c) introducing of group is similar to the mode in the reaction scheme 16, promptly carries out alkylation or arylation by the compound with formula 37.Representative R
5(d) group comprises for example cyano group, alkylthio and halogen.
Reaction scheme 17
Shown in reaction scheme 18, described method is particularly useful for 1-(2-pyridyl) pyrazole carboxylic acid of preparation formula 23e.2 of the pyrazoles of formula 39 and formula 37a, the reaction of 3-dihalo pyridine, generation has the 1-pyridyl pyrazoles of the formula 40a of good yield, and it has good desired zone chemical property.The 1-of the metallization of aforesaid formula 40a compound and carboxylation production 23e (2-pyridyl) pyrazole carboxylic acid.
Reaction scheme 18
Reaction scheme 19 has been described pyrazoles synthetic of formula 4c.But the optional substituted phenyl hydrazine of their through types 41 and the acetonylacetone hydrochlorate of formula 42 react the pyrazoles ester of production 43 and prepare.The pyrazoles acid of the hydrolysis production 23d of described ester.This method is for preparation R wherein
5(c) be to choose substituted phenyl wantonly and R
5(d) be that the compound of haloalkyl is particularly useful.
Reaction scheme 19
Reaction scheme 20 has been described another selective synthetic method of the pyrazoles acid of formula 23d.The 3+2 cycloaddition of the acrylate of the ntrilimine that they can be by suitable replacement and the replacement propiolate of formula 45 or formula 47 prepares.Need additional oxygenizement with the cycloaddition of acrylate, make the intermediate antipyrine be oxidized to pyrazoles.The pyrazoles acid of ester hydrolysis production 23d.The preferred imino-halide that is used for this reaction comprise the trifluoromethyl imino-choride of formula 48 and formula 49 together with two bromo imines (iminodibromide).Compound as 48 be known (J.Heterocycl.Chem.1985,22 (2), 565-8).Compound can obtain (TetrahedronLetters 1999,40,2605) by currently known methods as 49.This method is for preparation R wherein
5(c) be to choose substituted phenyl wantonly and R
5(d) be that the compound of haloalkyl or bromine is particularly useful.
Reaction scheme 20 The initial pyrazoles of formula 39 is compound known.The pyrazoles of formula 39a (compound of formula 39, wherein R
5(d) be CF
3) be commercially available.The pyrazoles of formula 39c (compound of formula 39, wherein R
5(d) be Cl or Br) can prepare by literature method (Chem.Ber.1966,99 (10), 3350-7).Another selective process useful of preparation compound 39c has been described in reaction scheme 21.Make the metallization of sulphonamide pyrazoles with n-Butyl Lithium, use hexachloroethane (R subsequently
5(d) be Cl) or 1,2-dibromo tetrachloroethane (R
5(d) for Br) carry out direct halogenation, the i.e. halide derivative of production 51.At room temperature remove sulfamoyl group with trifluoracetic acid (TFA) and carry out very fully, productive rate is good, thus the pyrazoles of production 39c.Those skilled in the art will know that formula 39c is the tautomer of formula 39b.
Reaction scheme 21
Should be appreciated that above-mentioned some reagent and the reaction conditions that is used for preparation formula I and formula II compound may be also incompatible with some functional group that intermediate exists.In these cases, introducing protection/deprotection procedure or functional group in building-up process changes mutually and will help to obtain required product.Using and selecting for the technician of chemosynthesis of blocking group is conspicuous (referring to for example Greene, T.W.; Wuts, P.G.M show " Protective Groupsin Organic Synthesis " (blocking group in the organic synthesis) second edition; Wiley:NewYork, 1991).Those skilled in the art will know, in some cases, (as described in any independent reaction scheme) may need to carry out the other conventional synthesis step for being described after introducing particular agent, with synthesizing of the compound of perfect I and II.Those skilled in the art it will also be appreciated that the compound for preparation formula I and II, may need the step described in the above-mentioned reaction scheme in conjunction with carrying out, and its order can be different with described concrete order.
Those skilled in the art it will also be appreciated that the compound of formula I described herein and II and intermediate can carry out that various parent's electricity, nucleophilic, free radical, metal are organic, oxidation and reduction reaction, carries out modification with the addition substituting group or to having substituting group now.
Need not to be described in further detail, the tool letter utilizes those skilled in the art of foregoing description to use the present invention in the scope the most completely at it.Therefore, following embodiment only should be considered as exemplary, and never in any form summary of the invention is limited.
1H NMR spectrum is obtained by the downfield record of tetramethylsilane with ppm: s is a singlet state, and d is a doublet, and t is a triplet state, and q is a quartet, and m is a multiplicity, and dd is the doublet of doublet, and dt is the doublet of triplet state, and br is wide singlet state, the m.p. fusing point.
Embodiment 1
Preparation N-methyl-N '-(2-bromo-4-fluorophenyl)-1,8-naphthalene-diformamide
Steps A: carbonyl preparation 8-[methylamino)]-the 1-naphthoic acid
At room temperature, to through stirring 1, (5g, N 25.3mmol) add methylamine (0.82g, N 26.5mmol), dinethylformamide (5mL) solution to the 8-naphthalic anhydride in dinethylformamide (50mL) solution.Reaction mixture was stirred 2.5 hours.Under reduced pressure remove and desolvate.Wash the thick solid that obtains therefrom with diethyl ether in a small amount, the line space of going forward side by side air dry, to generate product (5g), it is analyzed through NMR and determines to contain the 8-[(methylamino-) carbonyl]-1-naphthoic acid and 1, the 8-naphthalic anhydride, ratio is about 7: 1.This material is used for subsequent reaction without being further purified.
1H NMR (DMSO-d6) δ: 2.77 (doublet, 3H), 7.55-7.65 (multiplicity, 3H), 7.83 (doublet, 1H), 8.03-8.12 (multiplicity, 2H), 8.39 (quartet, 1H).
Step B: preparation N-methyl-N '-(2-bromo-4-fluorophenyl)-1,8-naphthalene-two formyl Amine
To 8-[(methylamino-through stirring, under nitrogen atmosphere, be cooled to about 5 ℃ described preparation of A set by step) carbonyl]-1-naphthoic acid (22.3g, 97.4mmol) and pyridine (15.4g, 0.195mol) methylene dichloride (300ml) solution in, the trifluoro-acetic anhydride that dropping is diluted in methylene dichloride (50ml) (22.5g, 0.107mol).After the dropping, at normal temperatures reaction mixture is further stirred half an hour.Filtering solid in a small amount.Under reduced pressure with filtrate simmer down to solid, (3 * 250ml) extract this solid with hot hexane.Hexane extract is merged, and under reduced pressure concentrate, produce 3-(methyl-imino)-1H, 3H-naphtho-[1,8-cd] is than muttering-1-ketone crude product (15g).
With thus obtained 3-(methyl-imino)-1H, and 3H-naphtho-[1,8-cd] pyrans-1-ketone (0.25g 1.19mmol) is dissolved in the methylene dichloride (3ml), and adding 2-bromo-4-fluoroaniline (0.17g, 1.45mmol).At room temperature stirred reaction mixture is 48 hours.Solid is filtered, collects, and in methylene dichloride, wash and carry out dry air, to produce the N-methyl N with methyl alcohol in a small amount '-(2-methyl-4-fluorophenyl)-1,8-naphthalene-diformamide (0.12g, fusing point are 249 ℃).
1H NMR (DMSO-d6) δ: 2.37 (singlet state, 3H), 2.72 (doublet, 3H), 7.05-7.12 (multiplicity, 2H), 7.54-7.64 (multiplicity, 3H), 7.75-7.83 (multiplicity, 2H), 8.05-8.10 (multiplicity, 2H), 8.33 (quartet, 1H), 9.84 (singlet state, 1H).
Embodiment 2
Preparation N-methyl 8-[(3, the 4-difluorophenyl) carbonylamino]-the 1-naphthoamide
Steps A: preparation N-methyl 8-nitro 1-naphthoamide
8-nitro-1-naphthoic acid under room temperature through stirring (1.5g, 6.9mmol), methylamine (0.22g, 7.3mmol) and imidazoles (0.68g, 8.3mmol) N, in dinethylformamide (12mL) solution, and the adding diethyl phosphorocyanidate (1.24g, 7.6mmol).Reaction mixture is stirred all night, pour in the water (100mL) and with vinyl acetic monomer (3 * 100mL) extractions.Merge ethyl acetate extraction liquid, dry on anhydrous magnesium sulfate, filter and under reduced pressure concentrate, to produce solid, this solid methanol wash in a small amount generates product (0.64g), and this product is utilized without being further purified.
1H NMR (DMSO-d6) δ: 2.76 (doublet, 3H), 7.72-8.37 (multiplicity, 6H), 8.66 (wide quartet, 1H).
Step B: preparation N-methyl 8-amido 1-naphthoamide
Under the 30psi hydrogen pressure, with palladium (10%, on gac) hydrogenation N-methyl 8-nitro-1-naphthoamide (0.5g, 2.17mmol) 1 hour of catalytic amount.Carry out suction strainer by C salt pair reaction mixture, and under reduced pressure concentrate, to generate product (0.42g), this product is utilized without being further purified.
1H NMR (DMSO-d6) δ: 2.82 (doublet, 3H), 5.46 (singlet state, 2H), 6.81-7.85 (multiplicity, 6H), 8.59 (wide quartet, 1H).
Step C: preparation N-methyl 8-[(3,4-difluorophenyl) carbonylamino]-the 1-naphthoamide
To the N-methyl 8-amido 1-naphthoamide through stirring (0.2g, 1mmol) and pyridine (0.24g, in methylene dichloride 3mmol) (10mL) solution, be added in batches actyl chloride in the methylene dichloride (2mL) (94.2mg, 1.2mmol).Mixture stirred 3 hours.Collect solid (110mg, fusing point are higher than 250 ℃) with suction strainer.
1H NMR (DMSO-d6) δ: 2.43 (doublet, 3H), 7.46-8.10 (multiplicity, 9H), 8.51 (wide quartet, 1H), 10.13 (singlet state, 1H).
Embodiment 3
Preparation N-methyl 8-[(2-thienyl) carbonylamino]-the 1-naphthoamide
To the N-methyl 8-amido 1-naphthoamide through stirring (0.2g, 1mmol) and pyridine (0.24g, in methylene dichloride 3mmol) (10mL) solution, be added in batches 2-thiophene carboxyl acyl chloride in the methylene dichloride (2mL) (176mg, 1.2mmol).Mixture stirred 3 hours.With dilute hydrochloric acid, saturated sodium bicarbonate aqueous solution and water order washing reaction mixture.Under reduced pressure part is removed and is desolvated.Collect the solid (36mg, fusing point are 210 ℃) that forms therefrom with suction strainer.
1H NMR (DMSO-d6) δ: 2.53 (doublet, 3H), 7.26-8.10 (multiplicity, 9H), 8.66 (wide quartet, 1H), 10.07 (singlet state, 1H).
By program described herein and method as known in the art, can prepare the compound of following table 1-10.Used following abbreviation: t be uncle in each table, s be secondary, and n is for just, and i is different, and c encircles, and Me is a methyl, Et is an ethyl, and Pr is a propyl group, and i-Pr is a sec.-propyl, and t-Bu is the tertiary butyl, and Ph is a phenyl, and OMe is a methoxyl group, OEt is an oxyethyl group, and SMe is the methyl sulfo-, and SEt is an ethylenebis dithiocarbamate, and CN is a cyano group, NO
2Be nitro, TMS is a trimethyl silyl, and S (O) Me is a methyl sulfinyl, and S (O)
2Me is a methyl sulphonyl.
Table 1
| R 3?? R 4? R 4b? R 5a? R 5b?Me???H?????Me????H?????CF 3?Me???H?????Me????H?????OCF 3?Et???H?????Me????H?????OCF 3?Me???H?????Me????Me????Br ?Me???H?????Me????Et????Br ?Me???H?????Me????Me????Cl ?Me???H?????Me????Et????Cl ?Me???H?????Me????Me????I ?Me???H?????Me????Me????CF 3?Me???H?????Me????Me????OCF 3?Et???H?????Me????Me????CF 3 | R 3??? R 4a? R 4b? R 5a? R 5b?Me????H?????H?????H?????CF 3?Me????H?????H?????H?????OCF 3?Et????H?????H?????H?????OCF 3?Me????H?????H?????Me????Br ?Me????H?????H?????Et????Br ?Me????H?????H?????Me????Cl ?Me????H?????H?????Er????Ct ?Me????H?????H?????Me????I ?Me????H?????H?????Me????CF 3?Me????H?????H?????Me????OCF 3?Et????H?????H?????Me????CF 3 |
| R 3?? R 4a? R 4b? R 5a?? R 5b?Me????H????Me????Me?????SCF 3?Me????H????Me????Me?????SCHF 2?Me????H????Me????Me?????OCHF 2?n-Pr??H????Me????Me?????CF 3?Me????H????Me????Me?????C 2F 5?Et????H????Me????Me?????C 2F 5?Me????H????Me????Et?????CF 3?Me????H????Me????n-Pr???CF 3?Me????H????Me????i-Pr???CF 3?Me????H????Me????Cl?????CF 3?Me????H????Me????F??????CF 3?Me????H????Me????Me?????SMe ?Me????H????Me????Me?????OMe ?Me????H????Me????Me?????OEt ?Me????H????Me????Me?????n-C 3F 7?Me????H????Me????Me?????i-C 3F 7?Me????H????Me????Me?????Et ?Me????H????Me????Me?????OCF 2CHF 2?Me????H????Me????Me?????SCF 2CHF 2?Me????H????Me????Me?????SO 2Me ?Me????H????Me????Me?????SO 2CF 3?Me????H????Me????CF 3???CF 3?Me????H????Me????CF 3???Me ?Me????H????Me????OMe????CF 3?Me????H????Me????H??????CF 3?Me????H????Me????H??????OCHF 2?Me????H????Me????H??????C 2F 5?Et????H????Me????H??????C 2F 5?Me????H????Me????H??????OCF 3?Me????H????Me????H??????OCF 2CHF 2?Me????H????Me????H??????SCF 2CHF 2?Me????H????Me????H??????n-C 3F 7?Me????H????Me????H??????i-C 3F 7?Me????H????Me????H??????Br ?Me????H????Me????H??????Cl ?Me????H????Me????H??????SCF 3?Me????H????Me????Ph?????CF 3 | R 3?? R 4a? R 4b R 5a? R 5b?Me????H????H????Me????SCF 3?Me????H????H????Me????SCHF 2?Me????H????H????Me????OCHF 2?n-Pr??H????H????Me????CF 3?Me????H????H????Me????C 2F 5?Et????H????H????Me????C 2F 5?Me????H????H????Et????CF 3?Me????H????H????n-Pr??CF 3?Me????H????H????i-Pr??CF 3?Me????H????H????Cl????CF 3?Me????H????H????F?????CF 3?Me????H????H????Me????SMe ?Me????H????H????Me????OMe ?Me????H????H????Me????CEt ?Me????H????H????Me????n-C 3F 7?Me????H????H????Me????i-C 3F 7?Me????H????H????Me????Et ?Me????H????H????Me????OCF 2CHF 2?Me????H????H????Me????SCF 2CHF 2?Me????H????H????Me????SO 2Me ?Me????H????H????Me????SO 2CF 3?Me????H????H????CF 3??CF 3?Me????H????H????CF 3??Me ?Me????H????H????OMe???CF 3?Me????H????H????H?????CF 3?Me????H????H????H?????OCHF 2?Me????H????H????H?????C 2F 5?Et????H????H????H?????C 2F 5?Me????H????H????H?????OCF 3?Me????H????H????H?????OCF 2CHF 2?Me????H????H????H?????SCF 2CHF 2?Me????H????H????H?????n-C 3F 7?Me????H????H????H?????i-C 3F 7?Me????H????H????H?????Br ?Me????H????H????H?????Cl ?Me????H????H????H?????SCF 3?Me????H????H????Ph????CF 3 |
| ??? R 3? R 4a? R 4b? R 5a????????? R 5bMe H Me Ph Cl Me H Me Ph Br Me H Me 2-pyridyl CF 3Me H Me 2-pyridyl Cl Me H Me 2-ClPh CF 3????Me????H????Me????2-ClPh????????OCF 3????Me????H????Me????2-ClPh????????Br ????Me????H????Me????2-ClPh????????Cl ????Me????H????Me????2-ClPh????????SCHF 2????Me????H????Me????2-BrPh????????CF 3????Me????H????Me????2-MePh????????CF 3????Me????H????Me????2-CNPh????????CF 3????Me????H????Me????2-FPh?????????CF 3????Me????H????Me????2,6-F 2Ph?????CF 3????Me????H????Me????2,4-F 2Ph?????CF 3????Me????H????Me????2,5-F 2Ph?????CF 3????Me????H????Me????2-MeOPh???????CF 3Me H Me 3-Cl-2-pyridyl CF 3Me H Me 3-Cl-2-pyridyl OCF 3Me H Me 3-Cl-2-pyridyl Br Me H Me 3-Cl-2-pyridyl Cl Me H Me 3-Cl-2-pyridyl SCHF 2Me H Me 3-F-2-pyridyl CF 3????Me????H????Me????3-CF 3-2-?????CF 3Pyridyl Me H Me 3-Me-2-CF 3Pyridyl Me H Me 3-Br-2-pyridyl CF 3Me H Me 3-Br-2-pyridyl OCF 3Me H Me 3-Br-2-pyridyl Br Me H Me 3-Br-2-pyridyl Cl Me Me H H CF 3????Me????Me???H?????H?????????????OCF 3????Et????Me???H?????H?????????????OCF 3????Me????Me???H?????Me????????????Br ????Me????Me???H?????Et????????????Br ????Me????Me???H?????Me????????????Cl | R 3? R 4a? R 4b?? R 5a???????????? R 5bMe H H Ph Cl Me H H Ph Br Me H H 2-pyridyl CF 3Me H H 2-pyridyl Cl Me H H 2-ClPh CF 3?Me????H????H?????2-ClPh???????????OCF 3?Me????H????H?????2-ClPh???????????Br ?Me????H????H?????2-ClPh???????????Cl ?Me????H????H?????2-ClPh???????????SCHF 2?Me????H????H?????2-BrPh???????????CF 3?Me????H????H?????2-MePh???????????CF 3?Me????H????H?????2-CNPh???????????CF 3?Me????H????H?????2-FPh????????????CF 3?Me????H????H?????2,6-F 2Ph????????CF 3?Me????H????H?????2,4-F 2Ph????????CF 3?Me????H????H?????2,5-F 2Ph????????CF 3?Me????H????H?????2-MeOPh??????????CF 3Me H H 3-Cl-2-pyridyl CF 3Me H H 3-Cl-2-pyridyl OCF 3Me H H 3-Cl-2-pyridyl Br Me H H 3-Cl-2-pyridyl Cl Me H H 3-Cl-2-pyridyl SCHF 2Me H H 3-F-2-pyridyl CF 3?Me????H????H?????3-CF 3-2-????????CF 3Pyridyl Me H H 3-Me-2-CF 3Pyridyl Me H H 3-Br-2-pyridyl CF 3Me H H 3-Br-2-pyridyl OCF 3Me H H 3-Br-2-pyridine radicals Br Me H H 3-Br-2-pyridine radicals Cl Me H Cl Et Br Me H Cl Me Cl Me H Cl Et Cl Me H Cl Me I Me H Cl Me CF3?Me????H????Cl????Me???????????????OCF 3 |
| ??? R 3?? R 4a? R 4b R 5a?? R 5b????Me????Me????H????Et?????Cl ????Me????Me????H????Me?????I ????Me????Me????H????Me?????CF 3????Me????Me????H????Me?????OCF 3????Et????Me????H????Me?????CF 3????Me????Me????H????Me?????SCF 3????Me????Me????H????Me?????SCHF 2????Me????Me????H????Me?????OCHF 2????n-Pr??Me????H????Me?????CF 3????Me????Me????H????Me?????C 2F 5????Et????Me????H????Me?????C 2F 5????Me????Me????H????Et?????CF 3????Me????Me????H????n-Pr???CF 3????Me????Me????H????i-Pr???CF 3????Me????Me????H????Cl?????CF 3????Me????Me????H????F??????CF 3????Me????Me????H????Me?????SMe ????Me????Me????H????Me?????OMe ????Me????Me????H????Me?????OEt ????Me????Me????H????Me?????n-C 3F 7????Me????Me????H????Me?????i-C 3F 7????Me????Me????H????Me?????Et ????Me????Me????H????Me?????OCF 2CHF 2????Me????Me????H????Me?????SCF 2CHF 2????Me????Me????H????Me?????SO 2Me ????Me????Me????H????Me?????SO 2CF 3????Me????Me????H????CF 3???CF 3????Me????Me????H????CF 3???Me ????Me????Me????H????OMe????CF 3????Me????Me????H????H??????CF 3????Me????Me????H????H??????OCHF 2????Me????Me????H????H??????C 2F 5????Et????Me????H????H??????C 2F 5????Me????Me????H????H??????OCF 3????Me????Me????H????H??????OCF 2CHF 2????Me????Me????H????H??????SCF 2CHF 2????Me????Me????H????H??????n-C 3F 7 | R 3?? R 4a? R 4b? R 5a??? R 5b?Et????H????Cl????Me??????CF 3?Me????H????Cl????Me??????SCF 3?Me????H????Cl????Me??????SCHF 2?Me????H????Cl????Me??????OCHF 2?n-Pr??H????Cl????Me??????CF 3?Me????H????Cl????Me??????C 2F 5?Et????H????Cl????Me??????C 2F 5?Me????H????Cl????Et??????CF 3?Me????H????Cl????n-Pr????CF 3?Me????H????Cl????i-Pr????CF 3?Me????H????Cl????Cl??????CF 3?Me????H????Cl????F???????CF 3?Me????H????Cl????Me??????SMe ?Me????H????Cl????Me??????OMe ?Me????H????Cl????Me??????OEt ?Me????H????Cl????Me??????n-C 3F 7?Me????H????Cl????Me??????i-C 3F 7?Me????H????Cl????Me??????Et ?Me????H????Cl????Me??????OCF 2CHF 2?Me????H????Cl????Me??????SCF 2CHF 2?Me????H????Cl????Me??????SO 2Me ?Me????H????Cl????Me??????SO 2CF 3?Me????H????Cl????CF 3????CF 3?Me????H????Cl????CF 3????Me ?Me????H????Cl????OMe?????CF 3?Me????H????Cl????H???????CF 3?Me????H????Cl????H???????OCHF 2?Me????H????Cl????H???????C 2F 5?Et????H????Cl????H???????C 2F 5?Me????H????Cl????H???????OCF 3?Me????H????Cl????H???????OCF 2CHF 2?Me????H????Cl????H???????SCF 2CHF 2?Me????H????Cl????H???????n-C 3F 7?Me????H????Cl????H???????i-C 3F 7?Me????H????Cl????H???????Br ?Me????H????Cl????H???????Cl ?Me????H????Cl????H???????SCF 3 |
| R 3? R 4a? R 4b R 5a????????????? R 5b?Me??Me????H????H????????????????i-C 3F 7?Me??Me????H????H????????????????Br ?Me??Me????H????H????????????????Cl ?Me??Me????H????H????????????????SCF 3?Me??Me????H????Ph???????????????CF 3Me Me H Ph Cl Me Me H Ph Br Me Me H 2-pyridyl CF 3Me Me H 2-pyridyl Cl Me Me H 2-ClPh CF 3?Me??Me????H????2-ClPh???????????OCF 3?Me??Me????H????2-ClPh???????????Br ?Me??Me????H????2-ClPh???????????Cl ?Me??Me????H????2-ClPh???????????SCHF 2?Me??Me????H????2-BrPh???????????CF 3?Me??Me????H????2-MePh???????????CF 3?Me??Me????H????2-CNPh???????????CF 3?Me??Me????H????2-FPh????????????CF 3?Me??Me????H????2,6-F 2Ph????????CF 3?Me??Me????H????2,4-F 2Ph????????CF 3?Me??Me????H????2,5-F 2Ph????????CF 3?Me??Me????H????2-MeOPh??????????CF 3Me Me H 3-Cl-2-pyridyl CF 3Me Me H 3-Cl-2-pyridyl OCF 3?Me??Me????H????3-CF 3-2-????????CF 3Pyridyl Me Me H 3-Me-2-CF 3Pyridyl Me Me H 3-Cl-2-pyridyl SCHF 2Me Me H 3-F-2-pyridyl CF 3Me Me H 3-Cl-2-pyridyl Br Me Me H 3-Cl-2-pyridyl Cl Me Me H 3-Br-2-pyridyl CF 3Me Me H 3-Br-2-pyridyl OCF 3Me Me h 3-Br-2-pyridyl Br Me Me H 3-Br-2-pyridyl Cl Me Cl H Me Br | R 3?? R 4a? R 4b? R 5a???????????? R 5b?Me????H????Cl????Ph???????????????CF 3Me H Cl Ph Cl Me H Cl Ph Br Me H Cl 2-pyridyl CF 3Me H Cl 2-pyridyl Cl Me H Cl 2-ClPh CF 3?Me????H????Cl????2-ClPh???????????OCF 3?Me????H????Cl????2-ClPh???????????Br ?Me????H????Cl????2-ClPh???????????Cl ?Me????H????Cl????2-ClPh???????????SCHF 2?Me????H????Cl????2-BrPh???????????CF 3?Me????H????Cl????2-MePh???????????CF 3?Me????H????Cl????2-CNPh???????????CF 3?Me????H????Cl????2-FPh????????????CF 3?Me????H????Cl????2,6-F 2Ph????????CF 3?Me????H????Cl????2,4-F 2Ph????????CF 3?Me????H????Cl????2,5-F 2Ph????????CF 3?Me????H????Cl????2-MeOPh??????????CF 3Me H Cl 3-Cl-2-pyridyl CF 3Me H Cl 3-Cl-2-pyridyl OCF3 Me H Cl 3-Cl-2-pyridyl Br Me H Cl 3-Cl-2-pyridyl Cl Me H Cl 3-Cl-2-pyridyl SCHF 2Me H Cl 3-F-2-pyridyl CF 3?Me????H????Cl????3-CF 3-2-????????CF 3Pyridyl Me H Cl 3-Me-2-CF 3Pyridyl Me H Cl 3-Br-2-pyridyl CF 3Me H Cl 3-Br-2-pyridyl OCF 3Me H Cl 3-Br-2-pyridyl Br Me H Cl 3-Br-2-pyridyl Cl Me Cl H Ph CF 3Me Cl H Ph Cl Me Cl H Ph Br Me Cl H 2-pyridyl CF 3Me Cl H 2-pyridyl Cl |
| R 3?? R 4a? R 4b? R 5a???? R 5b?Me????Cl????H????Et???????Br ?Me????Cl????H????Me???????Cl ?Me????Cl????H????Et???????Cl ?Me????Cl????H????Me???????I ?Me????Cl????H????Me???????CF 3?Me????Cl????H????Me???????OCF 3?Et????Cl????H????Me???????CF 3?Me????Cl????H????Me???????SCF 3?Me????Cl????H????Me???????SCHF 2?Me????Cl????H????Me???????OCHF 2?n-Pr??Cl????H????Me???????CF 3?Me????Cl????H????Me???????C 2F 5?Et????Cl????H????Me???????C 2F 5?Me????Cl????H????Et???????CF 3?Me????Cl????H????n-Pr?????CF 3?Me????Cl????H????i-Pr?????CF 3?Me????Cl????H????Cl???????CF 3?Me????Cl????H????F????????CF 3?Me????Cl????H????Me???????SMe ?Me????Cl????H????3-Me-2-??CF 3Pyridyl Me Cl H Me OEt Me Cl H Me n-C 3F 7?Me????Cl????H????Me???????i-C 3F 7?Me????Cl????H????Me???????Et ?Me????Cl????H????Me???????OCF 2CHF 2?Me????Cl????H????Me???????SCF 2CHF 2?Me????Cl????H????Me???????SO 2Me ?Me????Cl????H????Me???????SO 2CF 3?Me????Cl????H????CF 3?????CF 3?Me????Cl????H????CF 3?????Me ?Me????Cl????H????OMe??????CF 3?Me????Cl????H????H????????CF 3?Me????Cl????H????H????????OCHF 2?Me????Cl????H????H????????C 2F 5?Et????Cl????H????H????????C 2F 5 | R 3?? R 4a? R 4b? R 5a?????????? R 5b?Me????Cl????H????2-ClPh?????????CF 3?Me????Cl????H????2-ClPh?????????OCF 3?Me????Cl????H????2-ClPh?????????Br ?Me????Cl????H????2-ClPh?????????Cl ?Me????Cl????H????2-ClPh?????????SCHF 2?Me????Cl????H????2-BrPh?????????CF 3?Me????Cl????H????2-MePh?????????CF 3?Me????Cl????H????2-CNPh?????????CF 3?Me????Cl????H????2-FPh??????????CF 3?Me????Cl????H????2,6-F 2Ph??????CF 3?Me????Cl??H??????2,4-F 2Ph??????CF 3?Me????Cl????H????2,5-F 2Ph??????CF 3?Me????Cl????H????2-MeOPh????????CF 3Me Cl H 3-Cl-2-pyridyl CF 3Me Cl H 3-Cl-2-pyridyl OCF 3Me Cl H 3-Cl-2-pyridyl Br Me Cl H 3-Cl-2-pyridyl Cl Me Cl H 3-Cl-2-pyridyl SCHF 2Me Cl H 3-F-2-pyridyl CF 3?Me????Cl????H????3-CF 3-2-??????CF 3Pyridyl Me Cl H 3-Br-2-pyridyl CF 3Me Cl H 3-Br-2-pyridyl OCF 3Me Cl H 3-Br-2-pyridyl Br Me Cl H 3-Br-2-pyridyl Cl Me Cl H H OCF 3?Me????Cl????H????H??????????????OCF 2CHF 2?Me????Cl????H????H??????????????SCF 2CHF 2?Me????Cl????H????H??????????????n-C 3F 7?Me????Cl????H????H??????????????i-C 3F 7?Me????Cl????H????H??????????????Br ?Me????Cl????H????H??????????????Cl ?Me????Cl????H????H??????????????SCF 3?Me????Cl????H????Ph?????????????CF 3?Me????Cl????H????Me?????????????OMe |
Table 2
| R 3? R 4a? R 4b?? R 5a? R 5b?Me????H????Me????H?????CF 3?Me????H????Me????H?????OCF 3?Et????H????Me????H?????OCF 3?Me????H????Me????Me????Br ?Me????H????Me????Et????Br ?Me????H????Me????Me????Cl ?Me????H????Me????Et????Cl ?Me????H????Me????Me????I ?Me????H????Me????Me????CF 3?Me????H????Me????Me????OCF 3?Et????H????Me????Me????CF 3?Me????H????Me????Me????SCF 3?Me????H????Me????Me????SCHF 2?Me????H????Me????Me????OCHF 2?n-Pr??H????Me????Me????CF 3?Me????H????Me????Me????C 2F 5?Et????H????Me????Me????C 2F 5?Me????H????Me????Et????CF 3?Me????H????Me????n-Pr??CF 3?Me????H????Me????i-Pr??CF 3?Me????H????Me????Cl????CF 3?Me????H????Me????F?????CF 3?Me????H????Me????Me????SMe ?Me????H????Me????Me????OMe ?Me????H????Me????Me????OEt ?Me????H????Me????Me????n-C 3F 7?Me????H????Me????Me????i-C 3F 7?Me????H????Me????Me????Et | R 3?? R 4a? R 4b R 5a? R 5b?Me????H????H????H?????CF 3?Me????H????H????H?????OCF 3?Et????H????H????H?????OCF 3?Me????H????H????Me????Br ?Me????H????H????Et????Br ?Me????H????H????Me????Cl ?Me????H????H????Et????Cl ?Me????H????H????Me????I ?Me????H????H????Me????CF 3?Me????H????H????Me????OCF 3?Et????H????H????Me????CF 3?Me????H????H????Me????SCF 3?Me????H????H????Me????SCHF 2?Me????H????H????Me????OCHF 2?n-Pr??H????H????Me????CF 3?Me????H????H????Me????C 2F 5?Et????H????H????Me????C 2F 5?Me????H????H????Et????CF 3?Me????H????H????n-Pr??CF 3?Me????H????H????i-Pr??CF 3?Me????H????H????Cl????CF 3?Me????H????H????F?????CF 3?Me????H????H????Me????SMe ?Me????H????H????Me????OMe ?Me????H????H????Me????OEt ?Me????H????H????Me????n-C 3F 7?Me????H????H????Me????i-C 3F 7?Me????H????H????Me????Et |
| ? R 3?? R 4a R 4b? R 5a???????? R 5b??Me????H????Me????Me??????????OCF 2CHF 2??Me????H????Me????Me??????????SCF 2CHF 2??Me????H????Me????Me??????????SO 2Me ??Me????H????Me????Me??????????SO 2CF 3??Me????H????Me????CF 3????????CF 3??Me????H????Me????CF 3????????Me ??Me????H????Me????OMe?????????CF 3??Me????H????Me????H???????????CF 3??Me????H????Me????H???????????OCHF 2??Me????H????Me????H???????????C 2F 5??Et????H????Me????H???????????C 2F 5??Me????H????Me????H???????????OCF 3??Me????H????Me????H???????????OCF 2CHF 2??Me????H????Me????H???????????SCF 2CHF 2??Me????H????Me????H???????????n-C 3F 7??Me????H????Me????H???????????i-C 3F 7??Me????H????Me????H???????????Br ??Me????H????Me????H???????????Cl ??Me????H????Me????H???????????SCF 3??Me????H????Me????Ph??????????CF 3Me H Me Ph Cl Me H Me Ph Br Me H Me 2-pyridyl CF 3Me H Me 2-pyridyl Cl Me H Me 2-ClPh CF 3??Me????H????Me????2-ClPh??????OCF 3??Me????H????Me????2-ClPh??????Br ??Me????H????Me????2-ClPh??????Cl ??Me????H????Me????2-ClPh??????SCHF 2??Me????H????Me????2-BrPh??????CF 3??Me????H????Me????2-MePh??????CF 3??Me????H????Me????2-CNPh??????CF 3??Me????H????Me????2-FPh???????CF 3??Me????H????Me????2,6-F 2Ph???CF 3??Me????H????Me????2,4-F 2Ph???CF 3??Me????H????Me????2,5-F 2Ph???CF 3??Me????H????Me????2-MeOPh?????CF 3 | ? R 3? R 4a? R 4b R 5a??????? R 5b??Me????H????H????Me?????????OCF 2CHF 2??Me????H????H????Me?????????SCF 2CHF 2??Me????H????H????Me?????????SO 2Me ??Me????H????H????Me?????????SO 2CF 3??Me????H????H????CF 3???????CF 3??Me????H????H????CF 3???????Me ??Me????H????H????OMe????????CF 3??Me????H????H????H??????????CF 3??Me????H????H????H??????????OCHF 2??Me????H????H????H??????????C 2F 5??Et????H????H????H??????????C 2F 5??Me????H????H????H??????????OCF 3??Me????H????H????H??????????OCF 2CHF 2??Me????H????H????H??????????SCF 2CHF 2??Me????H????H????H??????????n-C 3F 7??Me????H????H????H??????????i-C 3F 7??Me????H????H????H??????????Br ??Me????H????H????H??????????Cl ??Me????H????H????H??????????SCF 3??Me????H????H????Ph?????????CF 3Me H H Ph Cl Me H H Ph Br Me H H 2-pyridyl CF 3Me H H 2-pyridyl Cl Me H H 2-ClPh CF 3??Me????H????H????2-ClPh?????OCF 3??Me????H????H????2-ClPh?????Br ??Me????H????H????2-ClPh?????Cl ??Me????H????H????2-ClPh?????SCHF 2??Me????H????H????2-BrPh?????CF 3??Me????H????H????2-MePh?????CF 3??Me????H????H????2-CNPh?????CF 3??Me????H????H????2-FPh??????CF 3??Me????H????H????2,6-F 2Ph??CF 3??Me????H????H????2,4-F 2Ph??CF 3??Me????H????H????2,5-F 2Ph??CF 3??Me????H????H????2-MeOPh????CF 3 |
| R 3?? R 4a? R 4b?? R 5a????????? R 5bMe H Me 3-Cl-2-pyridyl CF 3Me H Me 3-Cl-2-pyridyl OCF 3Me H Me 3-Cl-2-pyridyl Br Me H Me 3-Cl-2-pyridyl Cl Me H Me 3-Cl-2-pyridyl SCHF 2Me H Me 3-F-2-pyridyl CF 3?Me????H????Me??3-CF 3-2-????????CF 3Pyridyl Me H Me 3-Me-2-CF 3Pyridyl Me H Me 3-Br-2-pyridyl CF 3Me H Me 3-Br-2-pyridyl OCF 3Me H Me 3-Br-2-pyridyl Br Me H Me 3-Br-2-pyridyl Cl Me Me H H CF 3?Me????Me???H???H????????????????OCF 3?Et????Me???H???H????????????????OCF 3?Me????Me???H???Me???????????????Br ?Me????Me???H???Et???????????????Br ?Me????Me???H???Me???????????????Cl ?Me????Me???H???Et???????????????Cl ?Me????Me???H???Me???????????????I ?Me????Me???H???Me???????????????CF 3?Me????Me???H???Me???????????????OCF 3?Et????Me???H???Me???????????????CF 3?Me????Me???H???Me???????????????SCF 3?Me????Me???H???Me???????????????SCHF 2?Me????Me???H???Me???????????????OCHF 2?n-Pr??Me???H???Me???????????????CF 3?Me????Me???H???Me???????????????C 2F 5?Et????Me???H???Me???????????????C 2F 5?Me????Me???H???Et???????????????CF 3?Me????Me???H???n-Pr?????????????CF 3?Me????Me???H???i-Pr?????????????CF 3?Me????Me???H???Cl???????????????CF 3?Me????Me???H???F????????????????CF 3?Me????Me???H???Me???????????????SMe | R 3?? R 4a? R 4b????? R 5a???????? R 5bMe H H 3-Cl-pyridyl CF 3Me H H 3-Cl-2-pyridyl OCF 3Me H H 3-Cl-2-pyridyl Br Me H H 3-Cl-2-pyridyl Cl Me H H 3-Cl-2-pyridyl SCHF 2Me H H 3-F-2-pyridyl CF 3?Me????H????H?????3-CF 3-2-????????CF 3Pyridyl Me H H 3-Me-2-CF 3Pyridyl Me H H 3-Br-2-pyridyl CF 3Me H H 3-Br-2-pyridyl OCF 3Me H H 3-Br-2-pyridine radicals Br Me H H 3-Br-2-pyridine radicals Cl Me H Cl Et Br Me H Cl Me Cl Me H Cl Et Cl Me H Cl Me I Me H Cl Me CF3?Me????H????Cl????Me???????????????OCF 3?Et????H????Cl????Me???????????????CF 3?Me????H????Cl????Me???????????????SCF 3?Me????H????Cl????Me???????????????SCHF 2?Me????H????Cl????Me???????????????OCHF 2?n-Pr??H????Cl????Me???????????????CF 3?Me????H????Cl????Me???????????????C 2F 5?Et????H????Cl????Me???????????????C 2F 5?Me????H????Cl????Et???????????????CF 3?Me????H????Cl????n-Pr?????????????CF 3?Me????H????Cl????i-Pr?????????????CF 3?Me????H????Cl????Cl???????????????CF 3?Me????H????Cl????F????????????????CF 3?Me????H????Cl????Me???????????????SMe ?Me????H????Cl????Me???????????????OMe ?Me????H????Cl????Me???????????????OEt ?Me????H????Cl????Me???????????????n-C 3F 7?Me????H????Cl????Me???????????????i-C 3F 7 |
| R 3? R 4a? R 4b R 5a????? R 5b?Me??Me????H????Me????????OMe ?Me??Me????H????Me????????OEt ?Me??Me????H????Me????????n-C 3F 7?Me??Me????H????Me????????i-C 3F 7?Me??Me????H????Me????????Et ?Me??Me????H????Me????????OCF 2CHF 2?Me??Me????H????Me????????SCF 2CHF 2?Me??Me????H????Me????????SO 2Me ?Me??Me????H????Me????????SO 2CF 3?Me??Me????H????CF 3??????CF 3?Me??Me????H????CF 3??????Me ?Me??Me????H????OMe???????CF 3?Me??Me????H????H?????????CF 3?Me??Me????H????H?????????OCHF 2?Me??Me????H????H?????????C 2F 5?Et??Me????H????H?????????C 2F 5?Me??Me????H????H?????????OCF 3?Me??Me????H????H?????????OCF 2CHF 2?Me??Me????H????H?????????SCF 2CHF 2?Me??Me????H????H?????????n-C 3F 7?Me??Me????H????H?????????i-C 3F 7?Me??Me????H????H?????????Br ?Me??Me????H????H?????????Cl ?Me??Me????H????H?????????SCF 3?Me??Me????H????Ph????????CF 3Me Me H Ph Cl Me Me H Ph Br Me Me H 2-pyridyl CF 3Me Me H 2-pyridyl Cl Me Me H 2-ClPh CF 3?Me??Me????H????2-ClPh????OCF 3?Me??Me????H????2-ClPh????Br ?Me??Me????H????2-ClPh????Cl ?Me??Me????H????2-ClPh????SCHF 2?Me??Me????H????2-BrPh????CF 3?Me??Me????H????2-MePh????CF 3?Me??Me????H????2-CNPh????CF 3 | R 3 R 4a? R 4b? R 5a???????? R 5b?Me??H????Cl????Me??????????Et ?Me??H????Cl????Me??????????OCF 2CHF 2?Me??H????Cl????Me??????????SCF 2CHF 2?Me??H????Cl????Me??????????SO 2Me ?Me??H????Cl????Me??????????SO 2CF 3?Me??H????Cl????CF 3????????CF 3?Me??H????Cl????CF 3????????Me ?Me??H????Cl????OMe?????????CF 3?Me??H????Cl????H???????????CF 3?Me??H????Cl????H???????????OCHF 2?Me??H????Cl????H???????????C 2F 5?Et??H????Cl????H???????????C 2F 5?Me??H????Cl????H???????????OCF 3?Me??H????Cl????H???????????OCF 2CHF 2?Me??H????Cl????H???????????SCF 2CHF 2?Me??H????Cl????H???????????n-C 3F 7?Me??H????Cl????H???????????i-C 3F 7?Me??H????Cl????H???????????Br ?Me??H????Cl????H???????????Cl ?Me??H????Cl????H???????????SCF 3?Me??H????Cl????Ph??????????CF 3Me H Cl Ph Cl Me H Cl Ph Br Me H Cl 2-pyridyl CF 3Me H Cl 2-pyridyl Cl Me H Cl 2-ClPh CF 3?Me??H????Cl????2-ClPh??????OCF 3?Me??H????Cl????2-ClPh??????Br ?Me??H????Cl????2-ClPh??????Cl ?Me??H????Cl????2-ClPh??????SCHF 2?Me??H????Cl????2-BrPh??????CF 3?Me??H????Cl????2-MePh??????CF 3?Me??H????Cl????2-CNPh??????CF 3?Me??H????Cl????2-FPh???????CF 3?Me??H????Cl????2,6-F 2Ph???CF 3?Me??H????Cl????2,4-F 2Ph???CF 3?Me??H????Cl????2,5-F 2Ph???CF 3 |
| R 3?? R 4a? R 4b?? R 5a??????????? R 5b?Me????Me????H????2-FPh????????????CF 3?Me????Me????H????2,6-F 2Ph????????CF 3?Me????Me????H????2,4-F 2Ph????????CF 3?Me????Me????H????2,5-F 2Ph????????CF 3?Me????Me????H????2-MeOPh??????????CF 3Me Me H 3-Cl-2-pyridyl CF 3Me Me H 3-Cl-2-pyridyl OCF 3?Me????Me????H????3-CF 3-2-????????CF 3Pyridyl Me Me H 3-Me-2-CF 3Pyridyl Me Me H 3-Cl-2-pyridyl SCHF 2Me Me H 3-F-2-pyridyl CF 3Me Me H 3-Cl-2-pyridyl Br Me Me H 3-Cl-2-pyridyl Cl Me Me H 3-Br-2-pyridyl CF 3Me Me H 3-Br-2-pyridyl OCF 3Me Me H 3-Br-2-pyridine radicals Br Me Me H 3-Br-2-pyridine radicals Cl Me Cl H Me Br Me Cl H Et Br Me Cl H Me Cl Me Cl H Et Cl Me Cl H Me I Me Cl H Me CF3?Me????Cl????H????Me???????????????OCF 3?Et????Cl????H????Me???????????????CF 3?Me????Cl????H????Me???????????????SCF 3?Me????Cl????H????Me???????????????SCHF 2?Me????Cl????H????Me???????????????OCHF 2?n-Pr??Cl????H????Me???????????????CF 3?Me????Cl????H????Me???????????????C 2F 5?Et????Cl????H????Me???????????????C 2F 5?Me????Cl????H????Et???????????????CF 3?Me????Cl????H????n-Pr?????????????CF 3?Me????Cl????H????i-Pr?????????????CF 3?Me????Cl????H????Cl???????????????CF 3 | R 3?? R 4a? R 4b??? R 5a?????????? R 5b?Me????H????Cl????2-MeOPh??????????CF 3Me H Cl 3-Cl-2-pyridyl CF 3Me H Cl 3-Cl-2-pyridyl OCF3 Me H Cl 3-Cl-2-pyridyl Br Me H Cl 3-Cl-2-pyridyl Cl Me H Cl 3-Cl-2-pyridyl SCHF 2Me H Cl 3-F-2-pyridyl CF 3?Me????H????Cl????3-CF 3-2-????????CF 3Pyridyl Me H Cl 3-Me-2-CF 3Pyridyl Me H Cl 3-Br-2-pyridyl CF 3Me H Cl 3-Br-2-pyridyl OCF 3Me H Cl 3-Br-2-pyridyl Br Me H Cl 3-Br-2-pyridyl Cl Me Cl H H OCF 3?Me????Cl???H?????H????????????????OCF 2CHF 2?Me????Cl???H?????H????????????????SCF 2CHF 2?Me????Cl???H?????H????????????????n-C 3F 7?Me????Cl???H?????H????????????????i-C 3F 7?Me????Cl???H?????H????????????????Br ?Me????Cl???H?????H????????????????Cl ?Me????Cl???H?????H????????????????SCF 3?Me????Cl???H?????Ph???????????????CF 3Me Cl H Ph Cl Me Cl H Ph Br Me Cl H 2-pyridyl CF 3Me Cl H 2-pyridyl Cl Me Cl H 2-ClPh CF 3?Me????Cl???H?????2-ClPh???????????OCF 3?Me????Cl???H?????2-ClPh???????????Br ?Me????Cl???H?????2-ClPh???????????Cl ?Me????Cl???H?????2-ClPh???????????SCHF 2?Me????Cl???H?????2-BrPh???????????CF 3?Me????Cl???H?????2-MePh???????????CF 3?Me????Cl???H?????2-CNPh???????????CF 3?Me????Cl???H?????2-FPh????????????CF 3 |
| ? R 3?? R 4a? R 4b R 5a???? R 5b??Me????Cl????H????F????????CF 3??Me????Cl????H????Me???????SMe ??Me????Cl????H????Me???????OMe ??Me????Cl????H????Me???????OEt ??Me????Cl????H????Me???????n-C 3F 7??Me????Cl????H????Me???????i-C 3F 7??Me????Cl????H????Me???????Et ??Me????Cl????H????Me???????OCF 2CHF 2??Me????Cl????H????Me???????SCF 2CHF 2??Me????Cl????H????Me???????SO 2Me ??Me????Cl????H????Me???????SO 2CF 3??Me????Cl????H????3-CF 3-2-CF 3Pyridyl Me Cl H CF 3?????Me ??Me????Cl????H????OMe??????CF 3??Me????Cl????H????H????????CF 3??Me????Cl????H????H????????OCHF 2??Me????Cl????H????H????????C 2F 5 | R 3?? R 4a? R 4b?? R 5a??????????? R 5b?Me????Cl????H????2,6-F 2Ph????????CF 3?Me????Cl????H????2,4-F 2Ph????????CF 3?Me????Cl????H????2,5-F 2Ph????????CF 3?Me????Cl????H????2-MeOPh??????????CF 3Me Cl H 3-Cl-2-pyridyl CF 3Me Cl H 3-Cl-2-pyridyl OCF 3Me Cl H 3-Cl-2-pyridyl Br Me Cl H 3-Cl-2-pyridyl Cl Me Cl H 3-Cl-2-pyridyl SCHF 2Me Cl H 3-F-2-pyridyl CF 3?Me????Cl????H????CF 3?????????????CF 3?Me????Cl????H????3-Me-2-??????????CF 3Pyridyl Me Cl H 3-Br-2-pyridyl CF 3Me Cl H 3-Br-2-pyridyl OCF 3Me Cl H 3-Br-2-pyridyl Br Me Cl H 3-Br-2-pyridyl Cl Et Cl H H C 2F 5 |
Table 3
| R 3?? R 4a? R 4b? R 5a R 5b?Me????H????Me????H????CF 3?Me????H????Me????H????OCF 3?Et????H????Me????H????OCF 3?Me????H????Me????Me???Br ?Me????H????Me????Et???Br ?Me????H????Me????Me???Cl ?Me????H????Me????Et???Cl ?Me????H????Me????Me???I ?Me????H????Me????Me???CF 3 | ? R 3?? R 4a R 4b? R 5a? R 5b??Me????H????H????H?????CF 3??Me????H????H????H?????OCF 3??Et????H????H????H?????OCF 3??Me????H????H????Me????Br ??Me????H????H????Et????Br ??Me????H????H????Me????Cl ??Me????H????H????Et????Cl ??Me????H????H????Me????I ??Me????H????H????Me????CF 3 |
| R 3?? R 4a? R 4b? R 5a? R 5b?Me????H????Me????Me????OCF 3?Et????H????Me????Me????CF 3?Me????H????Me????Me????SCF 3?Me????H????Me????Me????SCHF 2?Me????H????Me????Me????OCHF 2?n-Pr??H????Me????Me????CF 3?Me????H????Me????Me????C 2F 5?Et????H????Me????Me????C 2F 5?Me????H????Me????Et????CF 3?Me????H????Me????n-Pr??CF 3?Me????H????Me????i-Pr??CF 3?Me????H????Me????Cl????CF 3?Me????H????Me????F?????CF 3?Me????H????Me????Me????SMe ?Me????H????Me????Me????OMe ?Me????H????Me????Me????OEt ?Me????H????Me????Me????n-C 3F 7?Me????H????Me????Me????i-C 3F 7?Me????H????Me????Me????Et ?Me????H????Me????Me????OCF 2CHF 2?Me????H????Me????Me????SCF 2CHF 2?Me????H????Me????Me????SO 2Me ?Me????H????Me????Me????SO 2CF 3?Me????H????Me????CF 3???CF 3?Me????H????Me????CF 3???Me ?Me????H????Me????OMe???CF 3?Me????H????Me????H?????CF 3?Me????H????Me????H?????OCHF 2?Me????H????Me????H?????C 2F 5?Et????H????Me????H?????C 2F 5?Me????H????Me????H?????OCF 3?Me????H????Me????H?????OCF 2CHF 2?Me????H????Me????H?????SCF 2CHF 2?Me????H????Me????H?????n-C 3F 7?Me????H????Me????H?????i-C 3F 7?Me????H????Me????H?????Br ?Me????H????Me????H?????Cl | R 3?? R 4a? R 4b R 5a? R 5b?Me????H????H????Me????OCF 3?Et????H????H????Me????CF 3?Me????H????H????Me????SCF 3?Me????H????H????Me????SCHF 2?Me????H????H????Me????OCHF 3?n-Pr??H????H????Me????CF 3?Me????H????H????Me????C 2F 5?Et????H????H????Me????C 2F 5?Me????H????H????Et????CF 3?Me????H????H????n-Pr??CF 3?Me????H????H????i-Pr??CF 3?Me????H????H????Cl????CF 3?Me????H????H????F?????CF 3?Me????H????H????Me????SMe ?Me????H????H????Me????OMe ?Me????H????H????Me????OEt ?Me????H????H????Me????n-C 3F 7?Me????H????H????Me????i-C 3F 7?Me????H????H????Me????Et ?Me????H????H????Me????OCF 2CHF 2?Me????H????H????Me????SCF 2CHF 2?Me????H????H????Me????SO 2Me ?Me????H????H????Me????SO 2CF 3?Me????H????H????CF 3??CF 3?Me????H????H????CF 3??Me ?Me????H????H????OMe???CF 3?Me????H????H????H?????CF 3?Me????H????H????H?????OCHF 2?Me????H????H????H?????C 2F 5?Et????H????H????H?????C 2F 5?Me????H????H????H?????CCF 3?Me????H????H????H?????OCF 2CHF 2?Me????H????H????H?????SCF 2CHF 2?Me????H????H????H?????n-C 3F 7?Me????H????H????H?????i-C 3F 7?Me????H????H????H?????Br ?Me????H????H????H?????Cl |
| ? R 3?? R 4a R 4b? R 5a???????????? R 5b??Me????H????Me????H????????????????SCF 3??Me????H????Me????Ph???????????????CF 3Me H Me Ph Cl Me H Me Ph Br Me H Me 2-pyridyl CF 3Me H Me 2-pyridyl Cl Me H Me 2-ClPh CF 3??Me????H????Me????2-ClPh???????????OCF 3??Me????H????Me????2-ClPh???????????Br ??Me????H????Me????2-ClPh???????????Cl ??Me????H????Me????2-ClPh???????????SCHF 2??Me????H????Me????2-BrPh???????????CF 3??Me????H????Me????2-MePh???????????CF 3??Me????H????Me????2-CNPh???????????CF 3??Me????H????Me????2-FPh????????????CF 3??Me????H????Me????2,6-F 2Ph????????CF 3??Me????H????Me????2,4-F 2Ph????????CF 3??Me????H????Me????2,5-F 2Ph????????CF 3??Me????H????Me????2-MeOPh??????????CF 3Me H Me 3-Cl-2-pyridyl CF 3Me H Me 3-Cl-2-pyridyl OCF 3Me H Me 3-Cl-2-pyridyl Br Me H Me 3-Cl-2-pyridyl Cl Me H Me 3Cl-2-pyridyl SCHF 2Me H Me 3-F-2-pyridyl CF 3??Me????H????Me????3-CF 3-2-????????CF 3Pyridyl Me H Me 3-Me-2-CF 3Pyridyl Me H Me 3-Br-2-pyridyl CF 3Me H Me 3-Br-2-pyridyl OCF 3Me H Me 3-Br-2-pyridyl Br Me H Me 3-Br-2-pyridyl Cl Me Me H H CF 3??Me????Me???H?????H????????????????OCF 3??Et????Me???H?????H????????????????OCF 3??Me????Me???H?????Me???????????????Br | R 3?? R 4a? R 4b R 5a???????????? R 5b?Me????H????H????H????????????????SCF 3?Me????H????H????Ph???????????????CF 3Me H H Ph Cl Me H H Ph Br Me H H 2-pyridyl CF 3Me H H 2-pyridyl Cl Me H H 2-ClPh CF 3?Me????H????H????2-ClPh???????????OCF 3?Me????H????H????2-ClPh???????????Br ?Me????H????H????2-ClPh???????????Cl ?Me????H????H????2-ClPh???????????SCHF 2?Me????H????H????2-BrPh???????????CF 3?Me????H????H????2-MePh???????????CF 3?Me????H????H????2-CNPh???????????CF 3?Me????H????H????2-FPh????????????CF 3?Me????H????H????2,6-F 2Ph????????CF 3?Me????H????H????2,4-F 2Ph????????CF 3?Me????H????H????2,5-F 2Ph????????CF 3?Me????H????H????2-MeOPh??????????CF 3Me H H 3-Cl-2-pyridyl CF 3Me H H 3-Cl-2-pyridyl OCF 3Me H H 3-Cl-2-pyridyl Br Me H H 3-Cl-2-pyridyl Cl Me H H 3-Cl-2-pyridyl SCHF 2Me H H 3-F-2-pyridyl CF 3?Me????H????H????3-CF 3-2-????????CF 3Pyridyl Me H H 3-Me-2-CF 3Pyridyl Me H H 3-Br-2-pyridyl CF 3Me H H 3-Br-2-pyridyl OCF 3Me H H 3-Br-2-pyridine radicals Br Me H H 3-Br-2-pyridine radicals Cl Me H Cl Et Br Me H Cl Me Cl Me H Cl Et Cl Me H Cl Me I |
| R 3?? R 4a? R 4b? R 5a? R 5b?Me????Me????H????Et????Br ?Me????Me????H????Me????Cl ?Me????Me????H????Et????Cl ?Me????Me????H????Me????I ?Me????Me????H????Me????CF 3?Me????Me????H????Me????OCF 3?Et????Me????H????Me????CF 3?Me????Me????H????Me????SCF 3?Me????Me????H????Me????SCHF 2?Me????Me????H????Me????OCHF 2?n-Pr??Me????H????Me????CF 3?Me????Me????H????Me????C 2F 5?Et????Me????H????Me????C 2F 5?Me????Me????H????Et????CF 3?Me????Me????H????n-Pr??CF 3?Me????Me????H????i-Pr??CF 3?Me????Me????H????Cl????CF 3?Me????Me????H????F?????CF 3?Me????Me????H????Me????SMe ?Me????Me????H????Me????OMe ?Me????Me????H????Me????OEt ?Me????Me????H????Me????n-C 3F 7?Me????Me????H????Me????i-C 3F 7?Me????Me????H????Me????Et ?Me????Me????H????Me????OCF 2CHF 2?Me????Me????H????Me????SCF 2CHF 2?Me????Me????H????Me????SO 2Me ?Me????Me????H????Me????SO 2CF 3?Me????Me????H????CF 3??CF 3?Me????Me????H????CF 3??Me ?Me????Me????H????OMe???CF 3?Me????Me????H????H?????CF 3?Me????Me????H????H?????OCHF 2?Me????Me????H????H?????C 2F 5?Et????Me????H????H?????C 2F 5?Me????Me????H????H?????OCF 3?Me????Me????H????H?????OCF 2CHF 2 | R 3?? R 4a? R 4b? R 5a? R 5b?Me????H????Cl????Me????CF 3?Me????H????Cl????Me????OCF 3?Et????H????Cl????Me????CF 3?Me????H????Cl????Me????SCF 3?Me????H????Cl????Me????SCHF 2?Me????H????Cl????Me????OCHF 2?n-Pr??H????Cl????Me????CF 3?Me????H????Cl????Me????C 2F 5?Et????H????Cl????Me????C 2F 5?Me????H????Cl????Et????CF 3?Me????H????Cl????n-Pr??CF 3?Me????H????Cl????i-Pr??CF 3?Me????H????Cl????Cl????CF 3?Me????H????Cl????F?????CF 3?Me????H????Cl????Me????SMe ?Me????H????Cl????Me????OMe ?Me????H????Cl????Me????OEt ?Me????H????Cl????Me????n-C 3F 7?Me????H????Cl????Me????i-C 3F 7?Me????H????Cl????Me????Et ?Me????H????Cl????Me????OCF 2CHF 2?Me????H????Cl????Me????SCF 2CHF 2?Me????H????Cl????Me????SO 2Me ?Me????H????Cl????Me????SO 2CF 3?Me????H????Cl????CF 3??CF 3?Me????H????Cl????CF 3??Me ?Me????H????Cl????OMe???CF 3?Me????H????Cl????H?????CF 3?Me????H????Cl????H?????OCHF 2?Me????H????Cl????H?????C 2F 5?Et????H????Cl????H?????C 2F 5?Me????H????Cl????H?????OCF 3?Me????H????Cl????H?????OCF 2CHF 2?Me????H????Cl????H?????SCF 2CHF 2?Me????H????Cl????H?????n-C 3F 7?Me????H????Cl????H?????i-C 3F 7?Me????H????Cl????H?????Br |
| R 3? R 4a? R 4b R 5a??????????????? R 5b?Me??Me????H????H????????????????SCF 2CHF 2?Me??Me????H????H????????????????n-C 3F 7?Me??Me????H????H????????????????i-C 3F 7?Me??Me????H????H????????????????Br ?Me??Me????H????H????????????????Cl ?Me??Me????H????H????????????????SCF 3?Me??Me????H????Ph???????????????CF 3Me Me H Ph Cl Me Me H Ph Br Me Me H 2-pyridyl CF 3Me Me H 2-pyridyl Cl Me Me H 2-ClPh CF 3?Me??Me????H????2-ClPh???????????OCF 3?Me??Me????H????2-ClPh???????????Br ?Me??Me????H????2-ClPh???????????Cl ?Me??Me????H????2-ClPh???????????SCHF 2?Me??Me????H????2-BrPh???????????CF 3?Me??Me????H????2-MePh???????????CF 3?Me??Me????H????2-CNPh???????????CF 3?Me??Me????H????2-FPh????????????CF 3?Me??Me????H????2,6-F 2Ph????????CF 3?Me??Me????H????2,4-F 2Ph????????CF 3?Me??Me????H????2,5-F 2Ph????????CF 3?Me??Me????H????2-MeOPh??????????CF 3Me Me H 3-Cl-2-pyridyl CF 3Me Me H 3-Cl-2-pyridyl OCF 3?Me??Me????H????3-CF 3-2-????????CF 3Pyridyl Me Me H 3-Me-2-CF 3Pyridyl Me Me H 3-Cl-2-pyridyl SCHF 2Me Me H 3-F-2-pyridyl CF 3Me Me H 3-Cl-2-pyridyl Br Me Me H 3-Cl-2-pyridyl Cl Me Me H 3-Br-2-pyridyl CF 3Me Me H 3-Br-2-pyridyl OCF 3Me Me H 3-Br-2-pyridyl Br | R 3?? R 4a? R 4b? R 5a???????????? R 5b?Me????H????Cl????H????????????????Cl ?Me????H????Cl????H????????????????SCF 3?Me????H????Cl????Ph???????????????CF 3Me H Cl Ph Cl Me H Cl Ph Br Me H Cl 2-pyridyl CF 3Me H Cl 2-pyridyl Cl Me H Cl 2-ClPh CF 3?Me????H????Cl????2-ClPh???????????OCF 3?Me????H????Cl????2-ClPh???????????Br ?Me????H????Cl????2-ClPh???????????Cl ?Me????H????Cl????2-ClPh???????????SCHF 2?Me????H????Cl????2-BrPh???????????CF 3?Me????H????Cl????2-MePh???????????CF 3?Me????H????Cl????2-CNPh???????????CF 3?Me????H????Cl????2-FPh????????????CF 3?Me????H????Cl????2,6-F 2Ph????????CF 3?Me????H????Cl????2,4-F 2Ph????????CF 3?Me????H????Cl????2,5-F 2Ph????????CF 3?Me????H????Cl????2-MeOPh??????????CF 3Me H Cl 3-Cl-2-pyridyl CF 3Me H Cl 3-Cl-2-pyridyl OCF3 Me H Cl 3-Cl-2-pyridyl Br Me H Cl 3-Cl-2-pyridyl Cl Me H Cl 3-Cl-2-pyridyl SCHF 2Me H Cl 3-F-2-pyridyl CF 3?Me????H????Cl????3-CF 3-2-????????CF 3Pyridyl Me H Cl 3-Me-2-CF 3Pyridyl Me H Cl 3-Br-2-pyridyl CF 3Me H Cl 3-Br-2-pyridyl OCF 3Me H Cl 3-Br-2-pyridyl Br Me H Cl 3-Br-2-pyridyl Cl Me Cl H H OCF 3?Me????Cl???H?????H????????????????OCF 2CHF 2?Me????Cl???H?????H????????????????SCF 2CHF 2 |
| R 3?? R 4a? R 4b R 5a????????? R 5bMe Me H 3-Br-2-pyridine radicals Cl Me Cl H Me Br Me Cl H Et Br Me Cl H Me Cl Me Cl H Et Cl Me Cl H Me I Me Cl H Me CF3?Me????Cl????H??Me????????????OCF 3?Et????Cl????H??Me????????????CF 3?Me????Cl????H??Me????????????SCF 3?Me????Cl????H??Me????????????SCHF 2?Me????Cl????H??Me????????????OCHF 2?n-Pr??Cl????H??Me????????????CF 3?Me????Cl????H??Me????????????C 2F 5?Et????Cl????H??Me????????????C 2F 5?Me????Cl????H??Et????????????CF 3?Me????Cl????H??n-Pr??????????CF 3?Me????Cl????H??i-Pr??????????CF 3?Me????Cl????H??Cl????????????CF 3?Me????Cl????H??F?????????????CF 3?Me????Cl????H??Me????????????SMe ?Me????Cl????H??Me????????????OMe ?Me????Cl????H??Me????????????OEt ?Me????Cl????H??Me????????????n-C 3F 7?Me????Cl????H??Me????????????i-C 3F 7?Me????Cl????H??Me????????????Et ?Me????Cl????H??Me????????????OCF 2CHF 2?Me????Cl????H??Me????????????SCF 2CHF 2?Me????Cl????H??Me????????????SO 2Me ?Me????Cl????H??Me????????????SO 2CF 3?Me????Cl????H??3-CF 3-2-?????CF 3Pyridyl Me Cl H CF 3??????????Me ?Me????Cl????H??OMe???????????CF 3?Me????Cl????H??H?????????????CF 3?Me????Cl????H??H?????????????OCHF 2?Me????Cl????H??H?????????????C 2F 5 | R 3?? R 4a? R 4b? R 5a????????????? R 5b?Me????Cl????H????H????????????????n-C 3F 7?Me????Cl????H????H????????????????i-C 3F 7?Me????Cl????H????H????????????????Br ?Me????Cl????H????H????????????????Cl ?Me????Cl????H????H????????????????SCF 3?Me????Cl????H????Ph???????????????CF 3Me Cl H Ph Cl Me Cl H Ph Br Me Cl H 2-pyridyl CF 3Me Cl H 2-pyridyl Cl Me Cl H 2-ClPh CF 3?Me????Cl????H????2-ClPh???????????OCF 3?Me????Cl????H????2-ClPh???????????Br ?Me????Cl????H????2-ClPh???????????Cl ?Me????Cl????H????2-ClPh???????????SCHF 2?Me????Cl????H????2-BrPh???????????CF 3?Me????Cl????H????2-MePh???????????CF 3?Me????Cl????H????2-CNPh???????????CF 3?Me????Cl????H????2-FPh????????????CF 3?Me????Cl????H????2,6-F 2Ph????????CF 3?Me????Cl????H????2,4-F 2Ph????????CF 3?Me????Cl????H????2,5-F 2Ph????????CF 3?Me????Cl????H????2-MeOPh??????????CF 3Me Cl H 3-Cl-2-pyridyl CF 3Me Cl H 3-Cl-2-pyridyl OCF 3Me Cl H 3-Cl-2-pyridyl Br Me Cl H 3-Cl-2-pyridyl Cl Me Cl H 3-Cl-2-pyridyl SCHF 2Me Cl H 3-F-2-pyridyl CF 3?Me????Cl????H????CF 3?????????????CF 3?Me????Cl????H????3-Me-2-??????????CF 3Pyridyl Me Cl H 3-Br-2-pyridyl CF 3Me Cl H 3-Br-2-pyridyl OCF 3Me Cl H 3-Br-2-pyridyl Br Me Cl H 3-Br-2-pyridyl Cl Et Cl H H C 2F 5 |
Table 4
| R 3?? R 4a? R 4b? R 5a? R 5b?Me????H????Me????H?????CF 3?Me????H????Me????H?????OCF 3?Et????H????Me????H?????OCF 3?Me????H????Me????Me????Br ?Me????H????Me????E?????Br ?Me????H????Me????Me????Cl ?Me????H????Me????Et????Cl ?Me????H????Me????Me????I ?Me????H????Me????Me????CF 3?Me????H????Me????Me????OCF 3?Et????H????Me????Me????CF 3?Me????H????Me????Me????SCF 3?Me????H????Me????Me????SCHF 2?Me????H????Me????Me????OCHF 2?n-Pr??H????Me????Me????CF 3?Me????H????Me????Me????C 2F 5?Et????H????Me????Me????C 2F 5?Me????H????Me????El????CF 3?Me????H????Me????B-Pr??CF 3?Me????H????Me????i-Pr??CF 3?Me????H????Me????i-Pr??OCF 3?Me????H????Me????Me????SMe ?Me????H????Me????Me????OMe ?Me????H????Me????Me????OEt ?Me????H????Me????Me????n-C 3F 7?Me????H????Me????Me????i-C 3F 7?Me????H????Me????Me????Et ?Me????H????Me????Me????OCF 2CHF 2 | R 3?? R 4a? R 4b? R 5a? R 5b?Me????H????H?????H?????CF 3?Me????H????H?????H?????OCF 3?Et????H????H?????H?????OCF 3?Me????H????H?????Me????Br ?Me????H????H?????Et????Br ?Me????H????H?????Me????Cl ?Me????H????H?????Et????Cl ?Me????H????H?????Me????I ?Me????H????H?????Me????CF 3?Me????H????H?????Me????OCF 3?Et????H????H?????Me????CF 3?Me????H????H?????Me????SCF 3?Me????H????H?????Me????SCHF 2?Me????H????H?????Me????OCHF 2?n-Pr??H????H?????Me????CF 3?Me????H????H?????Me????C 2F 5?Et????H????H?????Me????C 2F 5?Me????H????H?????Et????CF 3?Me????H????H?????n-Pr??CF 3?Me????H????H?????i-Pr??CF 3?Me????H????H?????Me????SMe ?Me????H????H?????Me????OMe ?Me????H????H?????Me????OEt ?Me????H????H?????Me????n-C 3F 7?Me????H????H?????Me????i-C 3F 7?Me????H????H?????Me????Et ?Me????H????tH????Me????OCF 2CHF 2?Me????H????H?????Me????SCF 2CHF 2 |
| R 3?? R 4a? R 4b? R 5a???????????? R 5b?Me????H????Me????Me???????????????SCF 2CHF 2?Me????H????Me????Me???????????????SO 2Me ?Me????H????Me????Me???????????????SO 2CF 3?Me????H????Me????CHF 2????????????CF 3?Me????H????Me????CHF 2????????????Me ?Me????H????Me????Ph???????????????CF 3Me H Me Ph Cl Me H Me Ph Br Me H Me 2-pyridyl CF 3Me H Me 2-pyridyl Cl Me H Me 2-ClPh CF 3?Me????H????Me????2-ClPh???????????OCF 3?Me????H????Me????2-ClPh???????????Br ?Me????H????Me????2-ClPh???????????Cl ?Me????H????Me????2-ClPh???????????SCHF 2?Me????H????Me????2-BrPh???????????CF 3?Me????H????Me????2-MePh???????????CF 3?Me????H????Me????2-CNPh???????????CF 3?Me????H????Me????2-FPh????????????CF 3?Me????H????Me????2,6-F 2Ph????????CF 3?Me????H????Me????2,4-F 2Ph????????CF 3?Me????H????Me????2,5-F 2Ph????????CF 3?Me????H????Me????2-MeOPh??????????CF 3Me H Me 3-Cl-2-pyridyl CF 3Me H Me 3-Cl-2-pyridyl OCF 3Me H Me 3-Cl-2-pyridyl Br Me H Me 3-Cl-2-pyridyl Cl Me H Me 3-Cl-2-pyridyl SCHF 2?Me????H????Me????3-CF 3-2-????????CF 3Pyridyl Me H Me 3-Me-2-CF 3Pyridyl Me H Me 3-F-2-pyridyl CF 3Me H Me 3-Br-2-pyridyl CF 3Me H Me 3-Br-2-pyridyl OCF 3Me H Me 3-Br-2-pyridyl Br Me H Me 3-Br-2-pyridyl Cl | R 3?? R 4a? R 4b R 5a???????????? R 5b?Me????H????H????Me???????????????SC 2Me ?Me????H????H????Me???????????????SO 2CF 3?Me????H????H????CF 3?????????????CF 3?Me????H????H????CF 3?????????????Me ?Me????H????H????Ph???????????????CF 3Me H H Ph Cl Me H H Ph Br Me H H 2-pyridyl CF 3Me H H 2-pyridyl Cl Me H H 2-ClPh CF 3?Me????H????H????2-ClPh???????????OCF 3?Me????H????H????2-ClPh???????????Br ?Me????H????H????2-ClPh???????????Cl ?Me????H????H????2-ClPh???????????SCHF 2?Me????H????H????2-BrPh???????????CF 3?Me????H????H????2-MePh???????????CF 3?Me????H????H????2-CNPh???????????CF 3?Me????H????H????2-FPh????????????CF 3?Me????H????H????2,6-F 2Ph????????CF 3?Me????H????H????2,4-F 2Ph????????CF 3?Me????H????H????2,5-F 2Ph????????CF 3?Me????H????H????2-MeOPh??????????CF 3Me H H 3-Cl-2-pyridyl CF 3Me H H 3-Cl-2-pyridyl OCF 3Me H H 3-Cl-2-pyridyl Br Me H H 3-Cl-2-pyridyl Cl Me H H 3-Cl-2-pyridyl SCHF 2Me H H 3-F-2-pyridyl CF 3?Me????H????H????3-CF 3-2-????????CF 3Pyridyl Me H H 3-Me-2-CF 3Pyridyl Me H H 3-Br-2-pyridyl CF 3Me H H 3-Br-2-pyridyl OCF 3Me H H 3-Br-2-pyridyl Br Me H H 3-Br-2-pyridyl Cl Me H Cl Et Br |
| R 3?? R 4a? R 4b? R 5a??? R 5b?Me????Me????H????Me??????Br ?Me????Me????H????E???????Br ?Me????Me????H????Me??????Cl ?Me????Me????H????Et??????Cl ?Me????Me????H????Me??????I ?Me????Me????H????Me??????CF 3?Me????Me????H????Me??????OCF 3?Et????Me????H????Me??????CF 3?Me????Me????H????Me??????SCF 3?Me????Me????H????Me??????SCHF 2?Me????Me????H????Me??????OCHF 2?n-Pr??Me????H????Me??????CF 3?Me????Me????H????Me??????C 2F 5?Et????Me????H????Me??????C 2F 5?Me????Me????H????Et??????CF 3?Me????Me????H????n-Pr????CF 3?Me????Me????H????i-Pr????CF 3?Me????Me????H????Me??????SMe ?Me????Me????H????Me??????OMe ?Me????Me????H????Me??????OEt ?Me????Me????H????Me??????n-C 3F 7?Me????Me????H????Me??????i-C 3F 7?Me????Me????H????Me??????Et ?Me????Me????H????Me??????OCF 2CHF 2?Me????Me????H????Me??????SCF 2CHF 2?Me????Me????H????Me??????SO 2Me ?Me????Me????H????Me??????SO 2CF 3?Me????Me????H????CF 3????CF 3?Me????Me????H????CF 3????Me ?Me????Me????H????Ph??????CF 3Me Me H Ph Cl Me Me H Ph Br Me Me H 2-pyridyl CF 3Me Me H 2-pyridyl Cl Me Me H 2-ClPh CF 3?Me????Me????H????2-ClPh??OCF 3?Me????Me????H????2-ClPh??Br | R 3?? R 4a? R 4b? R 5a????? R 5b?Me????H????Cl????Me????????Cl ?Me????H????Cl????Et????????Cl ?Me????H????Cl????Me????????I ?Me????H????Cl????Me????????CF 3?Me????H????Cl????Me????????OCF 3?Et????H????Cl????Me????????CF 3?Me????H????Cl????Me????????SCF 3?Me????H????Cl????Me????????SCHF 2?Me????H????Cl????Me????????OCHF 2?n-Pr??H????Cl????Me????????CF 3?Me????H????Cl????Me????????C 2F 5?Et????H????Cl????Me????????C 2F 5?Me????H????Cl????Et????????CF 3?Me????H????Cl????n-Pr??????CF 3?Me????H????Cl????i-Pr??????CF 3?Me????H????Cl????Me????????SMe ?Me????H????Cl????Me????????OMe ?Me????H????Cl????Me????????OEt ?Me????H????Cl????Me????????n-C 3F 7?Me????H????Cl????Me????????i-C 3F 7?Me????H????Cl????Me????????Et ?Me????H????Cl????Me????????OCF 2CHF 2?Me????H????Cl????Me????????SCF 2CHF 2?Me????H????Cl????Me????????SO 2Me ?Me????H????Cl????Me????????SO 2CF 3?Me????H????Cl????CF 3??????CF 3?Me????H????Cl????CF 3??????Me ?Me????H????Cl????Ph????????CF 3Me H Cl Ph Cl Me H Cl Ph Br Me H Cl 2-pyridyl CF 3Me H Cl 2-pyridyl Cl Me H Cl 2-ClPh CF 3?Me????H????Cl????2-ClPh????OCF 3?Me????H????Cl????2-ClPh????Br ?Me????H????Cl????2-ClPh????Cl ?Me????H????Cl????2-ClPh????SCHF 2 |
| ? R 3?? R 4a? R 4b? R 5a??????????? R 5b??Me????Me????H????2-ClPh???????????Cl ??Me????Me????H????2-ClPh???????????SCHF 2??Me????Me????H????2-BrPh???????????CF 3??Me????Me????H????2-MePh???????????CF 3??Me????Me????H????2-CNPh???????????CF 3??Me????Me????H????2-FPh????????????CF 3??Me????Me????H????2,6-F 2Ph????????CF 3??Me????Me????H????2,4-F 2Ph????????CF 3??Me????Me????H????2,5-F 2Ph????????CF 3??Me????Me????H????2-MeOPh??????????CF 3Me Me H 3-Cl-2-pyridyl CF 3Me Me H 3-Cl-2-pyridyl OCF 3Me Me H 3-Cl-2-pyridyl Br Me Me H 3-Cl-2-pyridyl Cl Me Me H 3-CF 3-2-????????CF 3Pyridyl Me Me H 3-Me-2-CF 3Pyridyl Me Me H 3-Cl-2-pyridyl SCHF 2Me Me H 3-F-2-pyridyl CF 3Me Me H 3-Br-2-pyridyl CF 3Me Me H 3-Br-2-pyridyl OCF 3Me Me H 3-Br-2-pyridine radicals Br Me Me H 3-Br-2-pyridine radicals Cl Me Cl H Me Br Me Cl H Et Br Me Cl H Me Cl Me Cl H Et Cl Me Cl H Me I Me Cl H Me CF3??Me????Cl????H????Me???????????????OCF 3??Et????Cl????H????Me???????????????CF 3??Me????Cl????H????Me???????????????SCF 3??Me????Cl????H????Me???????????????SCHF 2??Me????Cl????H????Me???????????????OCHF 2??n-Pr??Cl????H????Me???????????????CF 3??Me????Cl????H????Me???????????????C 2F 5 | ? R 3? R 4a?? R 4b?? R 5a??????? R 5b??Me????H?????Cl???2-BrPh????????CF 3??Me????H?????Cl???2-MePh????????CF 3??Me????H?????Cl???2-CNPh????????CF 3??Me????H?????Cl???2-FPh?????????CF 3??Me????H?????Cl???2,6-F 2Ph?????CF 3??Me????H?????Cl???2,4-F 2Ph?????CF 3??Me????H?????Cl???2,5-F 2Ph?????CF 3??Me????H?????Cl???2-OMe?????????CF 3Me H Cl 3-Cl-2-pyridyl CF 3Me H Cl 3-Cl-2-pyridyl OCF 3Me H Cl 3-Cl-2-pyridyl Br Me H Cl 3-Cl-2-pyridyl Cl Me H Cl 3-Cl-2-pyridyl SCHF 2Me H Cl 3-F-2-pyridyl CF 3??Me????H?????Cl???3-CF 3-2-?????CF 3Pyridyl Me H Cl 3-Me-2-CF 3Pyridyl Me H Cl 3-Br-2-pyridyl CF 3Me H Cl 3-Br-2-pyridyl OCF 3Me H Cl 3-Br-2-pyridyl Br Me H Cl 3-Br-2-pyridyl Cl Me Cl H Et CF 3??Me????Cl????H????n-Pr??????????CF 3??Me????Cl????H????i-Pr??????????CF 3??Me????Cl????H????Me????????????SMe ??Me????Cl????H????Me????????????OMe ??Me????Cl????H????Me????????????OEt ??Me????Cl????H????Me????????????n-C 3F 7??Me????Cl????H????Me????????????i-C 3F 7??Me????Cl????H????Me????????????Et ??Me????Cl????H????Me????????????OCF 2CHF 2??Me????Cl????H????Me????????????SCF 2CHF 2??Me????Cl????H????Me????????????SO 2Me ??Me????Cl????H????Me????????????SO 2CF 3??Me????Cl????H????CF 3??????????CF 3??Me????Cl????H????CF 3??????????Me |
| R 3?? R 4a? R 4b? R 5a???????????? R 5b?Et????Cl????H????Me???????????????C 2F 5Me Cl H 3-Cl-2-pyridyl CF 3Me Cl H 3-Cl-2-pyridyl OCF 3Me Cl H 3-Cl-2-pyridyl Br Me Cl H 3-Cl-2-pyridyl Cl Me Cl H 3-Cl-2-pyridyl SCHF 2Me Cl H 3-F-2-pyridyl CF 3?Me????Cl????H????3-CF 3-2-????????CF 3Pyridyl Me Cl H 3-Br-2-pyridyl CF 3Me Cl H 3-Br-2-pyridyl OCF 3Me Cl H 3-Br-2-pyridyl Br Me Cl H 3-Br-2-pyridyl Cl Me Cl H 2,4-F 2Ph????????CF 3?Me????Cl????H????2,5-F 2Ph????????CF 3?Me????Cl????H????2-OMe????????????CF 3?Me????Cl????H????2-ClPh???????????Br | ? R 3?? R 4a? R 4b R 5a???????? R 5b??Me????Cl????H????OMe?????????CF 3??Me????Cl????H????Ph??????????CF 3Me Cl H Ph Cl Me Cl H Ph Br Me Cl H 2-pyridyl CF 3Me Cl H 2-pyridyl Cl Me Cl H 2-ClPh CF 3??Me????Cl????H????3-Me-2-?????CF 3Pyridyl Me Cl H 2-ClPh Cl Me Cl H 2-ClPh SCHF 2??Me????Cl????H????2-BrPh??????CF 3??Me????Cl????H????2-MePh??????CF 3??Me????Cl????H????2-CNPh??????CF 3??Me????Cl????H????2-FPh???????CF 3??Me????Cl????H????2,6-F 2Ph???CF 3??Me????Cl????H????2-ClPh??????OCF 3 |
Table 5
| R 3?? R 4a? R 4b? R 5a? R 5b?Me????H????Me????H?????CHF 2?Me????H????Me????H?????CH 2CF 3?Et????H????Me????H?????CH 2CF 3?Me????H????Me????Me????CH 2CF 3?Me????H????Me????Et????CH 2CF 3?Me????H????Me????Me????CF 2CHF 2?Me????H????Me????Et????CHF 2?Me????H????Me????Me????CHF 2?Me????H????Me????Me????CBrF 2?Me????H????Me????Me????CH 2 | ? R 3?? R 4a R 4b? R 5a? R 5b??Me????H????H????H?????CHF 2??Me????H????H????H?????CH 2CF 3??Et????H????H????H?????CH 2CF 3??Me????H????H????Me????CH 2CF 3??Me????H????H????Et????CH 2CF 3??Me????H????H????Me????CF 2CHF 2??Me????H????H????Et????CHF 2??Me????H????H????Me????CHF 2??Me????H????H????Me????CBrF 2??Me????H????H????Me????CHF 2 |
| ? R 3? R 4a? R 4b? R 5a? R 5b??Et????H????Me????Me????CH 2CF 3??Me????H????Me????Me????Et ??Me????H????Me????Me????n-Pr ??Me????H????Me????Me????CH 2C 2F 5??n-Pr??H????Me????Me????CH 2CF 3??Me????H????Me????Me????CF 3??Et????H????Me????Me????C 2F 5??Me????H????Me????Et????CHF 2??Me????H????Me????n-Pr??CH 2CF 3??Me????H????Me????i-Pr??CHF 2??Me????H????Me????Cl????CH 2CF 3??Me????H????Me????F?????CH 2CF 3??Me????H????Me????Me????CH 2Cl ??Me????H????Me????Me????CClF 2??Me????H????Me????Me????CH 2CH 2Cl ??Me????H????Me????Me????n-C 3F 7??Me????H????Me????Me????i-C 3F 7??Me????H????Me????Me????Allyl ??Me????H????Me????Et????CF 2CHF 2??Me????H????Me????Et????i-C 3F 7??Me????H????Me????i-Pr??CF 2CHF 2??Me????H????Me????n-Pr??CF 2CHF 2??Me????H????Me????CF 3??CF 2CHF 2??Me????H????Me????CF 3??Me ??Me????H????Me????OMe???CH 2CF 3??Me????H????Me????H?????CH 2CF 3??Me????H????Me????H?????CH 2CF 3??Me????H????Me????H?????C 2F 5??Et????H????Me????H?????C 2F 5??Me????H????Me????H?????C 2F 5??Me????H????Me????H?????CF 2CHF 2??Me????H????Me????i-Pr??CH 2CF 3??Me????H????Me????H?????n-C 3F 7??Me????H????Me????H?????i-C 3F 7??Me????H????Me????Ph????CH 2CF 3??Me????H????Me????Ph????CF 2CHF 2??Me????H????Me????Ph????CF 3 | R 3?? R 4a? R 4b R 5a? R 5b?Et????H????H????Me????CH 2CF 3?Me????H????H????Me????Et ?Me????H????H????Me????n-Pr ?Me????H????H????Me????CH 2C 2F 5?n-Pr??H????H????Me????CH 2CF 3?Me????H????H????Me????CF 3?Et????H????H????Me????C 2F 5?Me????H????H????Et????CHF 2?Me????H????H????n-Pr??CH 2CF 3?Me????H????H????i-Pr??CHF 2?Me????H????H????Cl????CH 2CF 3?Me????H????H????F?????CH 2CF 3?Me????H????H????Me????CH 2Cl ?Me????H????H????Me????CClF 2?Me????H????H????Me????CH 2CH 2Cl ?Me????H????H????Me????n-C 3F 7?Me????H????H????Me????i-C 3F 7?Me????H????H????Me????Allyl ?Me????H????H????Me????CF 2CHF 2?Me????H????H????Me????i-C 3F 7?Me????H????H????Me????CF 2CHF 2?Me????H????H????Me????CF 2CHF 2?Me????H????H????CF 3??CF 2CHF 2?Me????H????H????CF 3??Me ?Me????H????H????OMe???CH 2CF 3?Me????H????H????H?????CH 2CF 3?Me????H????H????H?????CH 2CF 3?Me????H????H????H?????C 2F 5?Et????H????H????H?????C 2F 5?Me????H????H????H?????C 2F 5?Me????H????H????H?????CF 2CHF 2?Me????H????H????H?????CH 2CF 3?Me????H????H????H?????n-C 3F 7?Me????H????H????H?????i-C 3F 7?Me????H????H????H?????CH 2CF 3?Me????H????H????H?????CF 2CHF 2?Me????H????H????H?????CHF 2 |
| R 3?? R 4a? R 4b? R 5a?????????? R 5bMe H Me 2-pyridyl CH 2CF 3Me H Me 2-pyridyl CF 2CHF 2?Me????H????Me????2-ClPh?????????CH 2CF 3?Me????H????Me????2-ClPh?????????CF 2CHF 2?Me????H????Me????2-ClPh?????????CHF 2?Me????H????Me????2-ClPh?????????Et ?Me????H????Me????2-ClPh?????????CBrF 2?Me????H????Me????2-BrPh?????????CH 2CF 3?Me????H????Me????2-MePh?????????CH 2CF 3?Me????H????Me????2-CNPh?????????CH 2CF 3?Me????H????Me????2-FPh??????????CH 2CF 3?Me????H????Me????2,6-F 2Ph??????CH 2CF 3?Me????H????Me????2,4-F 2Ph??????CH 2CF 3?Me????H????Me????2,5-F 2Ph??????CH 2CF 3?Me????H????Me????2-MeOPh????????CH 2CF 3Me H Me 3-Cl-2-pyridyl CH 2CF 3Me H Me 3-Cl-2-pyridyl CF 2CHF 2Me H Me 3-Cl-2-pyridyl CF 3Me H Me 3-Cl-2-pyridyl CHF 2Me H Me 3-Cl-2-pyridyl CBrF 2Me H Me 3-F-2-pyridyl CH 2CF 3?Me????H????Me????3-CF 3-2-??????CH 2CF 3Pyridyl Me H Me 3-Me-2-CH 2CF 3Pyridyl Me H Me 3-Br-2-pyridyl CF 3Me H Me 3-Br-2-pyridyl CH 2CF 3Me H Me 3-Br-2-pyridyl CF 2CHF 2Me H Me 3-Br-2-pyridyl CClF 2?Me????Me???H?????H??????????????CHF 2?Me????Me???H?????H??????????????CH 2CF 3?Et????Me???H?????H??????????????CH 2CF 3?Me????Me???H?????Me?????????????CH 2CF 3?Me????Me???H?????Et?????????????CH 2CF 3?Me????Me???H?????Me?????????????CF 2CHF 2?Me????Me???H?????Et?????????????CHF 2?Me????Me???H?????Me?????????????CHF 2 | R 3?? R 4a? R 4b R 5a???????????? R 5b?Me????H????H????Ph??????????????CH 2CF 3?Me????H????H????Ph??????????????CF 2CHF 2?Me????H????H????Ph??????????????CH 2CF 3Me H H 2-pyridyl CF 2CHF 2Me H H 2-pyridyl CHF 2?Me????H????H????2-ClPh??????????Et ?Me????H????H????2-ClPh??????????CBrF 2?Me????H????H????2-ClPh??????????CH 2CF 3?Me????H????H????2-ClPh??????????CH 2CF 3?Me????H????H????2-ClPh??????????CH 2CF 3?Me????H????H????2-BrPh??????????CH 2CF 3?Me????H????H????2-MePh??????????CH 2CF 3?Me????H????H????2-CNPh??????????CH 2CF 3?Me????H????H????2-FPh???????????CH 2CF 3?Me????H????H????2,6-F 2Ph???????CH 2CF 3?Me????H????H????2,4-F 2Ph???????CH 2CF 3?Me????H????H????2,5-F 2Ph???????CF 2CHF 2?Me????H????H????2-MeO?Ph????????CF 3Me H H 3-Cl-2-pyridyl CHF 2Me H H 3-Cl-2-pyridyl CBrF 2Me H H 3-Cl-2-pyridyl CH 2CF 3?Me????H????H????3-CF 3-2-???????CH 2CF 3Pyridyl Me H H 3-Me-2-CF 2CHF 2Pyridyl Me H H 3-F-2-pyridyl CF 3Me H H 3-Cl-2-pyridyl CH 2CF 3Me H H 3-Cl-2-pyridyl CH 2CF 3Me H H 3-Br-2-pyridyl CClF 2Me H H 3-Br-2-pyridyl CH 2CF 3Me H H 3-Br-2-pyridyl CF 3Me H H 3-Br-2-pyridyl CF 3?Me????H????Cl???Et??????????????CHF 2?Me????H????Cl???Me??????????????CH 2CF 3?Me????H????Cl???Et??????????????CH 2CF 3?Me????H????Cl???Me??????????????CH 2CF 3?Me????H????Cl???Me??????????????CH 2CF 3 |
| R 3?? R 4a? R 4b? R 5a?? R 5b?Me????Me????H????Me?????CBrF 2?Me????Me????H????Me?????CHF 2?Et????Me????H????Me?????CH 2CF 3?Me????Me????H????Me?????Et ?Me????Me????H????Me?????n-Pr ?Me????Me????H????Me?????CH 2C 2F 5?n-Pr??Me????H????Me?????CH 2CF 3?Me????Me????H????Me?????CF 3?Et????Me????H????Me?????C 2F 5?Me????Me????H????Et?????CHF 2?Me????Me????H????n-Pr???CH 2CF 3?Me????Me????H????i-Pr???CHF 2?Me????Me????H????Cl?????CH 2CF 3?Me????Me????H????F??????CH 2CF 3?Me????Me????H????Me?????CH 2Cl ?Me????Me????H????Me?????CClF 2?Me????Me????H????Me?????CH 2CH 2Cl ?Me????Me????H????Me?????n-C 3F 7?Me????Me????H????Me?????i-C 3F 7?Me????Me????H????Me?????Allyl ?Me????Me????H????Me?????CF 2CHF 2?Me????Me????H????Me?????i-C 3F 7?Me????Me????H????Me?????CF 2CHF 2?Me????Me????H????Me?????CF 2CHF 2?Me????Me????H????CF 3???CF 2CHF 2?Me????Me????H????CF 3???Me ?Me????Me????H????OMe????CH 2CF 3?Me????Me????H????H??????CH 2CF 3?Me????Me????H????H??????CH 2CF 3?Me????Me????H????H??????C 2F 5?Et????Me????H????H??????C 2F 5?Me????Me????H????H??????C 2F 5?Me????Me????H????H??????CF 2CHF 2?Me????Me????H????H??????CH 2CF 3?Me????Me????H????H??????n-C 3F 7?Me????Me????H????H??????i-C 3F 7?Me????Me????H????H??????CH 2CF 3 | R 3?? R 4a? R 4b? R 5a? R 5b?Me????H????Cl????Me????CF 2CHF 2?Et????H????Cl????Me????CHF 2?Me????H????Cl????Me????CHF 2?Me????H????Cl????Me????CBrF 2?Me????H????Cl????Me????CHF 2?n-Pr??H????Cl????Me????CH 2CF 3?Me????H????Cl????Me????Et ?Et????H????Cl????Me????n-Pr ?Me????H????Cl????Et????CH 2C 2F 5?Me????H????Cl????n-Pr??CH 2CF 3?Me????H????Cl????i-Pr??CF 3?Me????H????Cl????Cl????C 2F 5?Me????H????Cl????F?????CHF 2?Me????H????Cl????Me????CH 2CF 3?Me????H????Cl????Me????CHF 2?Me????H????Cl????Me????CH 2CF 3?Me????H????Cl????Me????CH 2CF 3?Me????H????Cl????Me????CH 2Cl ?Me????H????Cl????Me????CClF 2?Me????H????Cl????Me????CH 2CH 2Cl ?Me????H????Cl????Me????n-C 3F 7?Me????H????Cl????Me????i-C 3F 7?Me????H????Cl????Me????Allyl ?Me????H????Cl????CF 3??CF 2CHF 2?Me????H????Cl????CF 3??i-C 3F 7?Me????H????Cl????OMe???CF 2CHF 2?Me????H????Cl????H?????CF 2CHF 2?Me????H????Cl????H?????CF 2CHF 2?Me????H????Cl????H?????Me ?Et????H????Cl????H?????CH 2CF 3?Me????H????Cl????H?????CH 2CF 3?Me????H????Cl????H?????CH 2CF 3?Me????H????Cl????H?????C 2F 5?Me????H????Cl????H?????C 2F 5?Me????H????Cl????H?????C 2F 5?Me????H????Cl????H?????CF 2CHF 2?Me????H????Cl????H?????CH 2CF 3 |
| ??? R 3?? R 4a? R 4b R 5a??????????? R 5b????Me????Me????H????H??????????????CF 2CHF 2????Me????Me????H????H??????????????CHF 2????Me????Me????H????Ph?????????????CH 2CF 3????Me????Me????H????Ph?????????????CF 2CHF 2????Me????Me????H????Ph?????????????CH 2CF 3Me Me H 2-pyridyl CF 2CHF 2Me Me H 2-pyridyl CHF 2????Me????Me????H????2-ClPh?????????Et ????Me????Me????H????2ClPh??????????CBrF 2????Me????Me????H????2-ClPh?????????CH 2CF 3????Me????Me????H????2-ClPh?????????CH 2CF 3????Me????Me????H????2-ClPh?????????CH 2CF 3????Me????Me????H????2-BrPh?????????CH 2CF 3????Me????Me????H????2-MePh?????????CH 2CF 3????Me????Me????H????2-CNPh?????????CH 2CF 3????Me????Me????H????2-FPh??????????CH 2CF 3????Me????Me????H????2,6-F 2Ph??????CH 2CF 3????Me????Me????H????2,4-F 2Ph??????CH 2CF 3????Me????Me????H????2,5-F 2Ph??????CF 2CHF 2????Me????Me????H????2-MeOPh????????CF 3Me Me H 3-Cl-2-pyridyl CHF 2Me Me H 3-Cl-2-pyridyl CBrF 2Me Me H 3-Cl-2-pyridyl CH 2CF 3Me Me H 3-Cl-2-pyridyl CH 2CF 3Me Me H 3-Cl-2-pyridyl CH 2CF 3Me Me H 3-F-2-pyridyl CF 3????Me????Me????H????3-CF 3-2-??????CH 2CF 3Pyridyl Me Me H 3-Me-2-CF 2CHF 2Pyridyl Me Me H 3-Br-2-pyridyl CClF 2Me Me H 3-Br-2-pyridyl CH 2CF 3Me Me H 3-Br-2-pyridyl CF 3Me Me H 3-Br-2-pyridyl CF 3????Me????Cl????H????Me?????????????CHF 2????Me????Cl????H????Et?????????????CH 2CF 3????Me????Cl????H????Me?????????????CH 2CF 3 | R 3?? R 4a? R 4b? R 5a?????????? R 5b?Me????H????Cl????H??????????????n-C 3F 7?Me????H????Cl????Ph?????????????i-C 3F 7?Me????H????Cl????Ph?????????????CH 2CF 3?Me????H????Cl????Ph?????????????CF 2CHF 2Me H Cl 2-pyridyl CHF 2Me H Cl 2-pyridyl CH 2CF 3?Me????H????Cl????2-ClPh?????????CF 2CHF 2?Me????H????Cl????2-ClPh?????????CH 2CF 3?Me????H????Cl????2-ClPh?????????CF 2CHF 2?Me????H????Cl????2-ClPh?????????CHF 2?Me????H????Cl????2-ClPh?????????Et ?Me????H????Cl????2-BrPh?????????CBrF 2?Me????H????Cl????2-MePh?????????CH 2CF 3?Me????H????Cl????2-CNPh?????????CH 2CF 3?Me????H????Cl????2-FPh??????????CH 2CF 3?Me????H????Cl????2,6-F 2Ph??????CH 2CF 3?Me????H????Cl????2,4-F 2Ph??????CH 2CF 3?Me????H????Cl????2,5-F 2Ph??????CH 2CF 3?Me????H????Cl????2-MeOPh????????CH 2CF 3Me H Cl 3-Cl-2-pyridyl CH 2CF 3Me H Cl 3-Cl-2-pyridyl CH 2CF 3Me H Cl 3-Cl-2-pyridyl CF 2CHF 2Me H Cl 3-Cl-2-pyridyl CF 3Me H Cl 3-Cl-2-pyridyl CHF 2Me H Cl 3-F-2-pyridyl CBrF 2Me H Cl 3-Br-2-pyridyl CH 2CF 3?Me????H????Cl????3-CF 3-2-??????CH 2CF 3Pyridyl Me H Cl 3-Me-2-CH 2CF 3Pyridyl Me H Cl 3-Br-2-pyridyl CF 3Me H Cl 3-Br-2-pyridyl CH 2CF 3Me H Cl 3-Br-2-pyridyl CF 2CHF 2?Me????Cl???H?????F??????????????CH 2CF 3?Me????Cl???H?????Me?????????????CHF 2?Me????Cl???H?????Me?????????????CH 2CF 3?Me????Cl???H?????Me?????????????CH 2CF 3 |
| R 3?? R 4a? R 4b? R 5a?????????? R 5b?Me????Cl????H????Et?????????????CH 2CF 3?Me????Cl????H????Me?????????????CH 2CF 3?Me????Cl????H????Me?????????????CF 2CHF 2?Me????Cl????H????Me?????????????CHF 2?Et????Cl????H????Me?????????????CHF 2?Me????Cl????H????Me?????????????CBrF 2?Me????Cl????H????Me?????????????CHF 2?Me????Cl????H????Me?????????????CH 2CF 3?n-Pr??Cl????H????Me?????????????Et ?Me????Cl????H????Me?????????????n-Pr ?Et????Cl????H????Me?????????????CH 2C 2F 5?Me????Cl????H????Et?????????????CH 2CF 3?Me????Cl????H????n-Pr???????????CF 3?Me????Cl????H????i-Pr???????????C 2F 5?Me????Cl????H????Cl?????????????CHF 2Me Cl H 3-Cl-2-pyridyl CH 2CF 3Me Cl H 3-Cl-2-pyridyl CF 2CHF 2Me Cl H 3-Cl-2-pyridyl CF 3Me Cl H 3-Cl-2-pyridyl CHF 2Me Cl H 3-Cl-2-pyridyl CBrF 2Me Cl H 3-F-2-pyridyl CH 2CF 3?Me????Cl????H????3-CF 3-2-??????CH 2CF 3Pyridyl Me Cl H 3-Br-2-pyridyl CF 3Me Cl H 3-Br-2-pyridyl CH 2CF 3Me Cl H 3-Br-2-pyridyl CF 2CHF 2Me Cl H 3-Br-2-pyridyl CClF 2?Me????Cl????H????2-ClPh?????????CHF 2?Me????Cl????H????2-ClPh?????????Et ?Me????Cl????H????2-ClPh?????????CBrF 2?Me????Cl????H????2-BrPh?????????CH 2CF 3?Me????Cl????H????2-MePh?????????CH 2CF 3?Me????Cl????H????2-CNPh?????????CH 2CF 3?Me????Cl????H????2-MeOPh????????CH 2CF 3?Me????Cl????H????2,5-F 2Ph??????CH 2CF 3 | R 3?? R 4a? R 4b? R 5a????? R 5b?Me????Cl????H????Me????????CH 2Cl ?Me????Cl????H????Me????????CClF 2?Me????Cl????H????Me????????CH 2CH 2Cl ?Me????Cl????H????Me????????n-C 3F 7?Me????Cl????H????Me????????i-C 3F 7?Me????Cl????H????Me????????Allyl ?Me????Cl????H????Me????????CF 2CHF 2?Me????Cl????H????CF 3??????i-C 3F 7?Me????Cl????H????CF 3??????CF 2CHF 2?Me????Cl????H????OMe???????CF 2CHF 2?Me????Cl????H????H?????????CF 2CHF 2?Me????Cl????H????H?????????Me ?Me????Cl????H????H?????????CH 2CF 3?Et????Cl????H????H?????????CH 2CF 3?Me????Cl????H????H?????????CH 2CF 3?Me????Cl????H????H?????????C 2F 5?Me????Cl????H????H?????????C 2F 5?Me????Cl????H????H?????????C 2F 5?Me????Cl????H????H?????????CF 2CHF 2?Me????Cl????H????H?????????CH 2CF 3?Me????Cl????H????H?????????n-C 3F 7?Me????Cl????H????3-Me-2-???CH 2CF 3Pyridyl Me Cl H H i-C 3F 7?Me????Cl????H????Ph????????CH 2CF 3?Me????Cl????H????Ph????????CF 2CHF 2?Me????Cl????H????Ph????????CHF 2Me Cl H 2-pyridyl CH 2CF 3Me Cl H 2-pyridyl CF 2CHF 2?Me????Cl????H????2-ClPh????CH 2CF 3?Me????Cl????H????2-ClPh????CF 2CHF 2?Me????Cl????H????2-FPh?????CH 2CF 3?Me????Cl????H????2,6-F 2Ph?CH 2CF 3?Me????Cl????H????2,4-F 2Ph?CH 2CF 3 |
Table 6
| R 3?? R 4a? R 4b? R 5a? R 5b?Me????H????Me????H?????CF 3?Me????H????Me????H?????OCF 3?Et????H????Me????H?????OCF 3?Me????H????Me????Me????Br ?Me????H????Me????Et????Br ?Me????H????Me????M?????Cl ?Me????H????Me????Et????Cl ?Me????H????Me????Me????I ?Me????H????Me????Me????CF 3?Me????H????Me????Me????OCF 3?Et????H????Me????Me????CF 3?Me????H????Me????Me????SCF 3?Me????H????Me????Me????SCHF 2?Me????H????Me????Me????OCHF 2?n-Pr??H????Me????Me????CF 3?Me????H????Me????Me????C 2F 5?Et????H????Me????Me????C 2F 5?Me????H????Me????Et????CF 3?Me????H????Me????n-Pr??CF 3?Me????H????Me????i-Pr??CF 3?Me????H????Me????Cl????CF 3?Me????H????Me????F?????CF 3?Me????H????Me????Me????SMe ?Me????H????Me????Me????OMe ?Me????H????Me????Me????OEt ?Me????H????Me????Me????n-C 3F 7?Me????H????Me????Me????i-C 3F 7?Me????H????Me????Me????Et | R 3?? R 4a? R 4b R 5a? R 5b?Me????H????H????H?????CF 3?Me????H????H????H?????OCF 3?Et????H????H????H?????OCF 3?Me????H????H????Me????Br ?Me????H????H????Et????Br ?Me????H????H????Me????Cl ?Me????H????H????Et????Cl ?Me????H????H????Me????I ?Me????H????H????Me????CF 3?Me????H????H????Me????OCF 3?Et????H????H????Me????CF 3?Me????H????H????Me????SCF 3?Me????H????H????Me????SCHF 2?Me????H????H????Me????OCHF 2?n-Pr??H????H????Me????CF 3?Me????H????H????Me????C 2F 5?Et????H????H????Me????C 2F 5?Me????H????H????Et????CF 3?Me????H????H????n-Pr??CF 3?Me????H????H????i-Pr??CF 3?Me????H????H????Cl????CF 3?Me????H????H????F?????CF 3?Me????H????H????Me????SMe ?Me????H????H????Me????OMe ?Me????H????H????Me????OEt ?Me????H????H????Me????n-C 3F 7?Me????H????H????Me????i-C 3F 7?Me????H????H????Me????Et |
| R 3?? R 4a? R 4b? R 5a??????? R 5b?Me????H????Me????Me??????????OCF 2CHF 2?Me????H????Me????Me??????????SCF 2CHF 2?Me????H????Me????Me??????????SO 2Me ?Me????H????Me????Me??????????SO 2CF 3?Me????H????Me????CF 3????????CF 3?Me????H????Me????CF 3????????Me ?Me????H????Me????OMe?????????CF 3?Me????H????Me????H???????????CF 3?Me????H????Me????H???????????OCHF 2?Me????H????Me????H???????????C 2F 5?Et????H????Me????H???????????C 2F 5?Me????H????Me????H???????????OCF 3?Me????H????Me????H???????????OCF 2CHF 2?Me????H????Me????H???????????SCF 2CHF 2?Me????H????Me????H???????????n-C 3F 7?Me????H????Me????H???????????i-C 3F 7?Me????H????Me????H???????????Br ?Me????H????Me????H???????????Cl ?Me????H????Me????H???????????SCF 3?Me????H????Me????Ph??????????CF 3Me H Me Ph Cl Me H Me Ph Br Me H Me 2-pyridyl CF 3Me H Me 2-pyridyl Cl Me H Me 2-ClPh CF 3?Me????H????Me????2-ClPh??????OCF 3?Me????H????Me????2-ClPh??????Br ?Me????H????Me????2-ClPh??????Cl ?Me????H????Me????2-ClPh??????SCHF 2?Me????H????Me????2-BrPh??????CF 3?Me????H????Me????2-MePh??????CF 3?Me????H????Me????2-CNPh??????CF 3?Me????H????Me????2-FPh???????CF 3?Me????H????Me????2,6-F 2Ph???CF 3?Me????H????Me????2,4-F 2Ph???CF 3?Me????H????Me????2,5-F 2Ph???CF 3?Me????H????Me????2-MeOPh?????CF 3 | R 3?? R 4a? R 4b R 5a??????? R 5b?Me????H????H????Me?????????OCF 2CHF 2?Me????H????H????Me?????????SCF 2CHF 2?Me????H????H????Me?????????SO 2Me ?Me????H????H????Me?????????SO 2CF 3?Me????H????H????CF 3???????CF 3?Me????H????H????CF 3???????Me ?Me????H????H????OMe????????CF 3?Me????H????H????H??????????CF 3?Me????H????H????H??????????OCHF 2?Me????H????H????H??????????C 2F 5?Et????H????H????H??????????C 2F 5?Me????H????H????H??????????OCF 3?Me????H????H????H??????????OCF 2CHF 2?Me????H????H????H??????????SCF 2CHF 2?Me????H????H????H??????????n-C 3F 7?Me????H????H????H??????????i-C 3F 7?Me????H????H????H??????????Br ?Me????H????H????H??????????Cl ?Me????H????H????H??????????SCF 3?Me????H????H????Ph?????????CF 3Me H H Ph Cl Me H H Ph Br Me H H 2-pyridyl CF 3Me H H 2-pyridyl Cl Me H H 2-ClPh CF 3?Me????H????H????2-ClPh?????OCF 3?Me????H????H????2-ClPh?????Br ?Me????H????H????2-ClPh?????Cl ?Me????H????H????2-ClPh?????SCHF 2?Me????H????H????2-BrPh?????CF 3?Me????H????H????2-MePh?????CF 3?Me????H????H????2-CNPh?????CF 3?Me????H????H????2-FPh??????CF 3?Me????H????H????2,6-F 2Ph??CF 3?Me????H????H????2,4-F 2Ph??CF 3?Me????H????H????2,5-F 2Ph??CF 3?Me????H????H????2-MeOPh????CF 3 |
| R 3??? R 4a? R 4b????? R 5a??????? R 5bMe H Me 3-Cl-2-pyridyl CF 3Me H Me 3-Cl-2-pyridyl OCF 3Me H Me 3-Cl-2-pyridyl Br Me H Me 3-Cl-2-pyridyl Cl Me H Me 3-Cl-2-pyridyl SCHF 2Me H Me 3-F-2-pyridyl CF 3?Me????H?????Me???3-CF 3-2-????????CF 3Pyridyl Me H Me 3-Me-2-CF 3Pyridyl Me H Me 3-Br-2-pyridyl CF 3Me H Me 3-Br-2-pyridyl OCF 3Me H Me 3-Br-2-pyridyl Br Me H Me 3-Br-2-pyridyl Cl Me Me H H CF 3?Me????Me????H????H????????????????OCF 3?Et????Me????H????H????????????????OCF 3?Me????Me????H????Me???????????????Br ?Me????Me????H????Et???????????????Br ?Me????Me????H????Me???????????????Cl ?Me????Me????H????Et???????????????Cl ?Me????Me????H????Me???????????????I ?Me????Me????H????Me???????????????CF 3?Me????Me????H????Me???????????????OCF 3?Et????Me????H????Me???????????????CF 3?Me????Me????H????Me???????????????SCF 3?Me????Me????H????Me???????????????SCHF 2?Me????Me????H????Me???????????????OCHF 2?n-Pr??Me????H????Me???????????????CF 3?Me????Me????H????Me???????????????C 2F 5?Et????Me????H????Me???????????????C 2F 5?Me????Me????H????Et???????????????CF 3?Me????Me????H????n-Pr?????????????CF 3?Me????Me????H????i-Pr?????????????CF 3?Me????Me????H????Cl???????????????CF 3?Me????Me????H????F????????????????CF 3?Me????Me????H????Me???????????????SMe | R 3?? R 4a? R 4b????? R 5a????? R 5bMe H H 3-Cl-2-pyridyl CF 3Me H H 3-Cl-2-pyridyl OCF 3Me H H 3-Cl-2-pyridyl Br Me H H 3-Cl-2-pyridyl Cl Me H H 3-Cl-2-pyridyl SCHF 2Me H H 3-F-2-pyridyl CF 3?Me????H????H????3-CF 3-2-??????CF 3Pyridyl Me H H 3-Me-2-CF 3Pyridyl Me H H 3-Br-2-pyridyl CF 3Me H H 3-Br-2-pyridyl OCF 3Me H H 3-Br-2-pyridine radicals Br Me H H 3-Br-2-pyridine radicals Cl Me H Cl Et Br Me H Cl Me Cl Me H Cl Et Cl Me H Cl Me I Me H Cl Me CF3?Me????H????Cl???Me?????????????CCF 3?Et????H????Cl???Me?????????????CF 3?Me????H????Cl???Me?????????????SCF 3?Me????H????Cl???Me?????????????SCHF 2?Me????H????Cl???Me?????????????OCHF 2?n-Pr??H????Cl???Me?????????????CF 3?Me????H????Cl???Me?????????????C 2F 5?Et????H????Cl???Me?????????????C 2F 5?Me????H????Cl???Et?????????????CF 3?Me????H????Cl???n-Pr???????????CF 3?Me????H????Cl???i-Pr???????????CF 3?Me????H????Cl???Cl?????????????CF 3?Me????H????Cl???F??????????????CF 3?Me????H????Cl???Me?????????????SMe ?Me????H????Cl???Me?????????????OMe ?Me????H????Cl???Me?????????????OEt ?Me????H????Cl???Me?????????????n-C 3F 7?Me????H????Cl???Me?????????????i-C 3F 7 |
| R 3? R 4a? R 4b R 5a?????? R 5b?Me??Me????H????Me????????OMe ?Me??Me????H????Me????????OEt ?Me??Me????H????Me????????n-C 3F 7?Me??Me????H????Me????????i-C 3F 7?Me??Me????H????Me????????Et ?Me??Me????H????Me????????OCF 2CHF 2?Me??Me????H????Me????????SCF 2CHF 2?Me??Me????H????Me????????SO 2Me ?Me??Me????H????Me????????SO 2CF 3?Me??Me????H????CF 3??????CF 3?Me??Me????H????CF 3??????Me ?Me??Me????H????OMe???????CF 3?Me??Me????H????H?????????CF 3?Me??Me????H????H?????????OCHF 2?Me??Me????H????H?????????C 2F 5?Et??Me????H????H?????????C 2F 5?Me??Me????H????H?????????OCF 3?Me??Me????H????H?????????OCF 2CHF 2?Me??Me????H????H?????????SCF 2CHF 2?Me??Me????H????H?????????n-C 3F 7?Me??Me????H????H?????????i-C 3F 7?Me??Me????H????H?????????Br ?Me??Me????H????H?????????Cl ?Me??Me????H????H?????????SCF 3?Me??Me????H????Ph????????CF 3Me Me H Ph Cl Me Me H Ph Br Me Me H 2-pyridyl CF 3Me Me H 2-pyridyl Cl Me Me H 2-ClPh CF 3?Me??Me????H????2-ClPh????OCF 3?Me??Me????H????2-ClPh????Br ?Me??Me????H????2-ClPh????Cl ?Me??Me????H????2-ClPh????SCHF 2?Me??Me????H????2-BrPh????CF 3?Me??Me????H????2-MePh????CF 3?Me??Me????H????2-CNPh????CF 3 | R 3?? R 4a? R 4b? R 5a????? R 5b?Me????H????Cl????Me????????Et ?Me????H????Cl????Me????????OCF 2CHF 2?Me????H????Cl????Me????????SCF 2CHF 2?Me????H????Cl????Me????????SO 2Me ?Me????H????Cl????Me????????SC 2CF 3?Me????H????Cl????CF 3??????CF 3?Me????H????Cl????CF 3??????Me ?Me????H????Cl????OMe???????CF 3?Me????H????Cl????H?????????CF 3?Me????H????Cl????H?????????OCHF 2?Me????H????Cl????H?????????C 2F 5?Et????H????Cl????H?????????C 2F 5?Me????H????Cl????H?????????OCF 3?Me????H????Cl????H?????????OCF 2CHF 2?Me????H????Cl????H?????????SCF 2CHF 2?Me????H????Cl????H?????????n-C 3F 7?Me????H????Cl????H?????????i-C 3F 7?Me????H????Cl????H?????????Br ?Me????H????Cl????H?????????Cl ?Me????H????Cl????H?????????SCF 3?Me????H????Cl????Ph????????CF 3Me H Cl Ph Cl Me H Cl Ph Br Me H Cl 2-pyridyl CF 3Me H Cl 2-pyridyl Cl Me H Cl 2-ClPh CF 3?Me????H????Cl????2-ClPh????OCF 3?Me????H????Cl????2-ClPh????Br ?Me????H????Cl????2-ClPh????Cl ?Me????H????Cl????2-ClPh????SCHF 2?Me????H????Cl????2-BrPh????CF 3?Me????H????Cl????2-MePh????CF 3?Me????H????Cl????2-CNPh????CF 3?Me????H????Cl????2-FPh?????CF 3?Me????H????Cl????2,6-F 2Ph?CF 3?Me????H????Cl????2,4-F 2Ph?CF 3?Me????H????Cl????2,5-F 2Ph?CF 3 |
| R 3?? R 4a? R 4b?? R 5a????????? R 5b?Me????Me????H????2-FPh??????????CF 3?Me????Me????H????2,6-F 2Ph??????CF 3?Me????Me????H????2,4-F 2Ph??????CF 3?Me????Me????H????2,5-F 2Ph??????CF 3?Me????Me????H????2-MeOPh????????CF 3Me Me H 3-Cl-2-pyridyl CF 3Me Me H 3-Cl-2-pyridyl OCF 3Me Me H 3-Cl-2-pyridyl Br Me Me H 3-Cl-2-pyridyl Cl Me Me H 3-Cl-2-pyridyl SCHF 2Me Me H 3-F-2-pyridyl CF 3?Me????Me????H????3-CF 3-2-??????CF 3Pyridyl Me Me H 3-Me-2-CF 3Pyridyl Me Me H 3-Br-2-pyridyl CF 3Me Me H 3-Br-2-pyridyl OCF 3Me Me H 3-Br-2-pyridine radicals Br Me Me H 3-Br-2-pyridine radicals Cl Me Cl H Me Br Me Cl H Et Br Me Cl H Me Cl Me Cl H Et Cl Me Cl H Me I Me Cl H Me CF3?Me????Cl????H????Me?????????????OCF 3?Et????Cl????H????Me?????????????CF 3?Me????Cl????H????Me?????????????SCF 3?Me????Cl????H????Me?????????????SCHF 2?Me????Cl????H????Me?????????????OCHF 2?n-Pr??Cl????H????Me?????????????CF 3?Me????Cl????H????Me?????????????C 2F 5?Et????Cl????H????Me?????????????C 2F 5?Me????Cl????H????Et?????????????CF 3?Me????Cl????H????n-Pr???????????CF 3?Me????Cl????H????i-Pr???????????CF 3?Me????Cl????H????Cl?????????????CF 3 | R 3?? R 4a? R 4b???? R 5a??????? R 5b?Me????H????Cl????2-MeOPh????????CF 3Me H Cl 3-Cl-2-pyridyl CF 3Me H Cl 3-Cl-2-pyridyl OCF3 Me H Cl 3-Cl-2-pyridyl Br Me H Cl 3-Cl-2-pyridyl Cl Me H Cl 3-Cl-2-pyridyl SCHF 2Me H Cl 3-F-2-pyridyl CF 3Me H Cl 3-Br-2-pyridyl CF 3Me H Cl 3-Br-2-pyridyl OCF 3Me H Cl 3-Br-2-pyridyl Br Me H Cl 3-Br-2-pyridyl Cl Me H Cl 3-CF 3-2-??????CF 3Pyridyl Me H Cl 3-Me-2-CF 3Pyridyl Me Cl H H OCF 3?Me????Cl????H????H??????????????OCF 2CHF 2?Me????Cl????H????H??????????????SCF 2CHF 2?Me????Cl????H????H??????????????n-C 3F 7?Me????Cl????H????H??????????????i-C 3F 7?Me????Cl????H????H??????????????Br ?Me????Cl????H????H??????????????Cl ?Me????Cl????H????H??????????????SCF 3?Me????Cl????H????Ph?????????????CF 3Me Cl H Ph Cl Me Cl H Ph Br Me Cl H 2-pyridyl CF 3Me Cl H 2-pyridyl Cl Me Cl H 2-ClPh CF 3?Me????Cl????H????2-ClPh?????????OCF 3?Me????Cl????H????2-ClPh?????????Br ?Me????Cl????H????2-ClPh?????????Cl ?Me????Cl????H????2-ClPh?????????SCHF 2?Me????Cl????H????2-BrPh?????????CF 3?Me????Cl????H????2-MePh?????????CF 3?Me????Cl????H????2-CNPh?????????CF 3?Me????Cl????H????2-FPh??????????CF 3 |
| R 3?? R 4a? R 4b? R 5a????? R 5b?Me????Cl????H????F?????????CF 3?Me????Cl????H????Me????????SMe ?Me????Cl????H????Me????????OMe ?Me????Cl????H????Me????????OEt ?Me????Cl????H????Me????????n-C 3F 7?Me????Cl????H????Me????????i-C 3F 7?Me????Cl????H????Me????????Et ?Me????Cl????H????Me????????OCF 2CHF 2?Me????Cl????H????Me????????SCF 2CHF 2?Me????Cl????H????Me????????SO 2Me ?Me????Cl????H????Me????????SO 2CF 3?Me????Cl????H????3-CF 3-2-?CF 3Pyridyl Me Cl H CF 3??????Me ?Me????Cl????H????OMe???????CF 3?Me????Cl????H????H?????????CF 3?Me????Cl????H????H?????????OCHF 2?Me????Cl????H????H?????????C 2F 5 | ? R 3 R 4a? R 4b?? R 5a??????????? R 5b??Me??Cl????H????2,6-F 2Ph????????CF 3??Me??Cl????H????2,4-F 2Ph????????CF 3??Me??Cl????H????2,5-F 2Ph????????CF 3??Me??Cl????H????2-MeOPh??????????CF 3Me Cl H 3-Cl-2-pyridyl CF 3Me Cl H 3-Cl-2-pyridyl OCF 3Me Cl H 3-Cl-2-pyridyl Br Me Cl H 3-Cl-2-pyridyl Cl Me Cl H 3-Cl-2-pyridyl SCHF 2Me Cl H 3-F-2-pyridyl CF 3??Me??Cl????H????CF 3?????????????CF 3??Me??Cl????H????3-Me-2-??????????CF 3Pyridyl Me Cl H 3-Br-2-pyridyl CF 3Me Cl H 3-Br-2-pyridyl OCF 3Me Cl H 3-Br-2-pyridyl Br Me Cl H 3-Br-2-pyridyl Cl Et Cl H H C 2F 5 |
Table 7
| R 3? R 4a? R 4b? R 5a?? R 5b?Me????H????Me????H?????CF 3?Me????H????Me????H?????OCF 3?Et????H????Me????H?????OCF 3?Me????H????Me????Me????Br ?Me????H????Me????Et????Br ?Me????H????Me????Me????Cl ?Me????H????Me????Et????Cl ?Me????H????Me????Me????I ?Me????H????Me????Me????CF 3 | ? R 3? R 4a? R 4b R 5a?? R 5b??Me????H????H????H?????CF 3??Me????H????H????H?????OCF 3??Et????H????H????H?????OCF 3??Me????H????H????Me????Br ??Me????H????H????Et????Br ??Me????H????H????Me????Cl ??Me????H????H????Et????Cl ??Me????H????H????Me????I ??Me????H????H????Me????CF 3 |
| ? R 3?? R 4a R 4b? R 5a? R 5b??Me????H????Me????Me???OCF 3??Et????H????Me????Me???CF 3??Me????H????Me????Me???SCF 3??Me????H????Me????Me???SCHF 2??Me????H????Me????Me???OCHF 2??n-Pr??H????Me????Me???CF 3??Me????H????Me????Me???C 2F 5??Et????H????Me????Me???C 2F 5??Me????H????Me????Et???CF 3??Me????H????Me????n-Pr?CF 3??Me????H????Me????i-Pr?CF 3??Me????H????Me????Cl???CF 3??Me????H????Me????F????CF 3??Me????H????Me????Me???SMe ??Me????H????Me????Me???OMe ??Me????H????Me????Me???OEt ??Me????H????Me????Me???n-C 3F 7??Me????H????Me????Me???i-C 3F 7??Me????H????Me????Me???Et ??Me????H????Me????Me???OCF 2CHF 2??Me????H????Me????Me???SCF 2CHF 2??Me????H????Me????Me???SO 2Me ??Me????H????Me????Me???SO 2CF 3??Me????H????Me????CF 3?CF 3??Me????H????Me????CF 3?Me ??Me????H????Me????OMe??CF 3??Me????H????Me????H????CF 3??Me????H????Me????H????OCHF 2??Me????H????Me????H????C 2F 5??Et????H????Me????H????C 2F 5??Me????H????Me????H????OCF 3??Me????H????Me????H????OCF 2CHF 2??Me????H????Me????H????SCF 2CHF 2??Me????H????Me????H????n-C 3F 7??Me????H????Me????H????i-C 3F 7??Me????H????Me????H????Br ??Me????H????Me????H????Cl | R 3?? R 4a? R 4b R 5a? R 5b?Me????H????H????Me???CCF 3?Et????H????H????Me???CF 3?Me????H????H????Me???SCF 3?Me????H????H????Me???SCHF 2?Me????H????H????Me???OCHF 2?n-Pr??H????H????Me???CF 3?Me????H????H????Me???C 2F 5?Et????H????H????Me???C 2F 5?Me????H????H????Et???CF 3?Me????H????H????n-Pr?CF 3?Me????H????H????i-Pr?CF 3?Me????H????H????Cl???CF 3?Me????H????H????F????CF 3?Me????H????H????Me???SMe ?Me????H????H????Me???OMe ?Me????H????H????Me???OEt ?Me????H????H????Me???n-C 3F 7?Me????H????H????Me???i-C 3F 7?Me????H????H????Me???Et ?Me????H????H????Me???OCF 2CHF 2?Me????H????H????Me???SCF 2CHF 2?Me????H????H????Me???SO 2Me ?Me????H????H????Me???SO 2CF 3?Me????H????H????CF 3?CF 3?Me????H????H????CF 3?Me ?Me????H????H????OMe??CF 3?Me????H????H????H????CF 3?Me????H????H????H????OCHF 2?Me????H????H????H????C 2F 5?Et????H????H????H????C 2F 5?Me????H????H????H????OCF 3?Me????H????H????H????OCF 2CHF 2?Me????H????H????H????SCF 2CHF 2?Me????H????H????H????n-C 3F 7?Me????H????H????H????i-C 3F 7?Me????H????H????H????Br ?Me????H????H????H????Cl |
| R 3?? R 4a? R 4b? R 5a?????????? R 5b?Me????H????Me????H??????????????SCF 3?Me????H????Me????Ph?????????????CF 3Me H Me Ph Cl Me H Me Ph Br Me H Me 2-pyridyl CF 3Me H Me 2-pyridyl Cl Me H Me 2-ClPh CF 3?Me????H????Me????2-ClPh?????????OCF 3?Me????H????Me????2-ClPh?????????Br ?Me????H????Me????2-ClPh?????????Cl ?Me????H????Me????2-ClPh?????????SCHF 2?Me????H????Me????2-BrPh?????????CF 3?Me????H????Me????2-MePh?????????CF 3?Me????H????Me????2-CNPh?????????CF 3?Me????H????Me????2-FPh??????????CF 3?Me????H????Me????2,6-F 2Ph??????CF 3?Me????H????Me????2,4-F 2Ph??????CF 3?Me????H????Me????2,5-F 2Ph??????CF 3?Me????H????Me????2-MeOPh????????CF 3Me H Me 3-Cl-2-pyridyl CF 3Me H Me 3-Cl-2-pyridyl OCF 3Me H Me 3-Cl-2-pyridyl Br Me H Me 3-Cl-2-pyridyl Cl Me H Me 3-Cl-2-pyridyl SCHF 2Me H Me 3-F-2-pyridyl CF 3?Me????H????Me????3-CF 3-2-??????CF 3Pyridyl Me H Me 3-Me-2-CF 3Pyridyl Me H Me 3-Br-2-pyridyl CF 3Me H Me 3-Br-2-pyridyl OCF 3Me H Me 3-Br-2-pyridyl Br Me H Me 3-Br-2-pyridyl Cl Me Me H H CF 3?Me????Me???H?????H??????????????OCF 3?Et????Me???H?????H??????????????OCF 3?Me????Me???H?????Me?????????????Br | R 3?? R 4a? R 4b R 5a???????????? R 5b?Me????H????H????H???????????????SCF 3?Me????H????H????Ph??????????????CF 3Me H H Ph Cl Me H H Ph Br Me H H 2-pyridyl CF 3Me H H 2-pyridyl Cl Me H H 2-ClPh CF 3?Me????H????H????2-ClPh??????????OCF 3?Me????H????H????2-ClPh??????????Br ?Me????H????H????2-ClPh??????????Cl ?Me????H????H????2-ClPh??????????SCHF 2?Me????H????H????2-BrPh??????????CF 3?Me????H????H????2-MePh??????????CF 3?Me????H????H????2-CNPh??????????CF 3?Me????H????H????2-FPh???????????CF 3?Me????H????H????2,6-F 2Ph???????CF 3?Me????H????H????2,4-F 2Ph???????CF 3?Me????H????H????2,5-F 2Ph???????CF 3?Me????H????H????2-MeOPh?????????CF 3Me H H 3-Cl-2-pyridyl CF 3Me H H 3-Cl-2-pyridyl OCF 3Me H H 3-Cl-2-pyridyl Br Me H H 3-Cl-2-pyridyl Cl Me H H 3-Cl-2-pyridyl SCHF 2Me H H 3-F-2-pyridyl CF 3?Me????H????H????3-CF 3-2-???????CF 3Pyridyl Me H H 3-Me-2-CF 3Pyridyl Me H H 3-Br-2-pyridyl CF 3Me H H 3-Br-2-pyridyl OCF 3Me H H 3-Br-2-pyridine radicals Br Me H H 3-Br-2-pyridine radicals Cl Me H Cl Et Br Me H Cl Me Cl Me H Cl Et Cl Me H Cl Me I |
| ??? R 3? R 4a? R 4b R 5a? R 5b????Me???Me????H????Et???Br ????Me???Me????H????Me???Cl ????Me???Me????H????Et???Cl ????Me???Me????H????Me???I ????Me???Me????H????Me???CF 3????Me???Me????H????Me???OCF 3????Et???Me????H????Me???CF 3????Me???Me????H????Me???SCF 3????Me???Me????H????Me???SCHF 2????Me???Me????H????Me???OCHF 2????n-Pr?Me????H????Me???CF 3????Me???Me????H????Me???C 2F 5????Et???Me????H????Me???C 2F 5????Me???Me????H????Et???CF 3????Me???Me????H????n-Pr?CF 3????Me???Me????H????i-Pr?CF 3????Me???Me????H????Cl???CF 3????Me???Me????H????F????CF 3????Me???Me????H????Me???SMe ????Me???Me????H????Me???OMe ????Me???Me????H????Me???OEt ????Me???Me????H????Me???n-C 3F 7????Me???Me????H????Me???i-C 3F 7????Me???Me????H????Me???Et ????Me???Me????H????Me???OCF 2CHF 2????Me???Me????H????Me???SCF 2CHF 2????Me???Me????H????Me???SO 2Me ????Me???Me????H????Me???SO 2CF 3????Me???Me????H????CF 3?CF 3????Me???Me????H????CF 3?Me ????Me???Me????H????OMe??CF 3????Me???Me????H????H????CF 3????Me???Me????H????H????OCHF 2????Me???Me????H????H????C 2F 5????Et???Me????H????H????C 2F 5????Me???Me????H????H????OCF 3????Me???Me????H????H????OCF 2CHF 2 | R 3?? R 4a? R 4b? R 5a? R 5b?Me????H????Cl????Me????CF 3?Me????H????Cl????Me????OCF 3?Et????H????Cl????Me????CF 3?Me????H????Cl????Me????SCF 3?Me????H????Cl????Me????SCHF 2?Me????H????Cl????Me????OCHF 2?n-Pr??H????Cl????Me????CF 3?Me????H????Cl????Me????C 2F 5?Et????H????Cl????Me????C 2F 5?Me????H????Cl????Et????CF 3?Me????H????Cl????n-Pr??CF 3?Me????H????Cl????i-Pr??CF 3?Me????H????Cl????Cl????CF 3?Me????H????Cl????F?????CF 3?Me????H????Cl????Me????SMe ?Me????H????Cl????Me????OMe ?Me????H????Cl????Me????OEt ?Me????H????Cl????Me????n-C 3F 7?Me????H????Cl????Me????i-C 3F 7?Me????H????Cl????Me????Et ?Me????H????Cl????Me????OCF 2CHF 2?Me????H????Cl????Me????SCF 2CHF 2?Me????H????Cl????Me????SO 2Me ?Me????H????Cl????Me????SO 2CF 3?Me????H????Cl????CF 3??CF 3?Me????H????Cl????CF 3??Me ?Me????H????Cl????OMe???CF 3?Me????H????Cl????H?????CF 3?Me????H????Cl????H?????OCHF 2?Me????H????Cl????H?????C 2F 5?Et????H????Cl????H?????C 2F 5?Me????H????Cl????H?????OCF 3?Me????H????Cl????H?????OCF 2CHF 2?Me????H????Cl????H?????SCF 2CHF 2?Me????H????Cl????H?????n-C 3F 7?Me????H????Cl????H?????i-C 3F 7?Me????H????Cl????H?????Br |
| ? R 3 R 4a? R 4b? R 5a???????????? R 5b??Me??Me????H????H????????????????SCF 2CHF 2??Me??Me????H????H????????????????n-C 3F 7??Me??Me????H????H????????????????i-C 3F 7??Me??Me????H????H????????????????Br ??Me??Me????H????H????????????????Cl ??Me??Me????H????H????????????????SCF 3??Me??Me????H????Ph???????????????CF 3Me Me H Ph Cl Me Me H Ph Br Me Me H 2-pyridyl CF 3Me Me H 2-pyridyl Cl Me Me H 2-ClPh CF 3??Me??Me????H????2-ClPh???????????OCF 3??Me??Me????H????2-ClPh???????????Br ??Me??Me????H????2-ClPh???????????Cl ??Me??Me????H????2-ClPh???????????SCHF 2??Me??Me????H????2-BrPh???????????CF 3??Me??Me????H????2-MePh???????????CF 3??Me??Me????H????2-CNPh???????????CF 3??Me??Me????H????2-FPh????????????CF 3??Me??Me????H????2,6-F 2Ph????????CF 3??Me??Me????H????2,4-F 2Ph????????CF 3??Me??Me????H????2,5-F 2Ph????????CF 3??Me??Me????H????2-MeOPh??????????CF 3Me Me H 3-Cl-2-pyridyl CF 3Me Me H 3-Cl-2-pyridyl OCF 3Me Me H 3-Cl-2-pyridyl Br Me H Cl 3-CF 3-2-????????CF 3Pyridyl Me Me H 3-Cl-2-pyridyl SCHF 2Me Me H 3-F-2-pyridyl CF 3??Me??Me????H????3-CF 3-2-????????CF 3Pyridyl Me H Cl 3-Br-2-pyridyl Br Me Me H 3-Br-2-pyridyl CF 3Me Me H 3-Br-2-pyridyl OCF 3Me Me H 3-Br-2-pyridyl Br | R 3?? R 4a? R 4b? R 5a?????????? R 5b?Me????H????Cl????H??????????????Cl ?Me????H????Cl????H??????????????SCF 3?Me????H????Cl????Ph?????????????CF 3Me H Cl Ph Cl Me H Cl Ph Br Me H Cl 2-pyridyl CF 3Me H Cl 2-pyridyl Cl Me H Cl 2-ClPh CF 3?Me????H????Cl????2-ClPh?????????OCF 3?Me????H????Cl????2-ClPh?????????Br ?Me????H????Cl????2-ClPh?????????Cl ?Me????H????Cl????2-ClPh?????????SCHF 2?Me????H????Cl????2-BrPh?????????CF 3?Me????H????Cl????2-MePh?????????CF 3?Me????H????Cl????2-CNPh?????????CF 3?Me????H????Cl????2-FPh??????????CF 3?Me????H????Cl????2,6-F 2Ph??????CF 3?Me????H????Cl????2,4-F 2Ph??????CF 3?Me????H????Cl????2,5-F 2Ph??????CF 3?Me????H????Cl????2-MeOPh????????CF 3Me H Cl 3-Cl-2-pyridyl CF 3Me H Cl 3-Cl-2-pyridyl OCF3 Me H Cl 3-Cl-2-pyridyl Br Me H Cl 3-Cl-2-pyridyl Cl Me H Cl 3-Cl-2-pyridyl SCHF 2Me H Cl 3-F-2-pyridyl CF 3Me Me H 3-Cl-2-pyridyl Cl Me H Cl 3-Me-2-CF 3Pyridyl Me H Cl 3-Br-2-pyridyl CF 3Me H Cl 3-Br-2-pyridyl OCF 3?Me????Me???H?????3-Me-2-????????CF 3Pyridyl Me H Cl 3-Br-2-pyridyl Cl Me Cl H H OCF 3?Me????Cl???H?????H??????????????OCF 2CHF 2?Me????Cl???H?????H??????????????SCF 2CHF 2 |
| R 3? R 4a? R 4b R 5a????????? R 5bMe Me H 3-Br-2-pyridine radicals Cl Me Cl H Me Br Me Cl H Et Br Me Cl H Me Cl Me Cl H Et Cl Me Cl H Me I Me Cl H Me CF3?Me???Cl???H???Me????????????OCF 3?Et???Cl???H???Me????????????CF 3?Me???Cl???H???Me????????????SCF 3?Me???Cl???H???Me????????????SCHF 2?Me???Cl???H???Me????????????OCHF 2?n-Pr?Cl???H???Me????????????CF 3?Me???Cl???H???Me????????????C 2F 5?Et???Cl???H???Me????????????C 2F 5?Me???Cl???H???Et????????????CF 3?Me???Cl???H???n-Pr??????????CF 3?Me???Cl???H???i-Pr??????????CF 3?Me???Cl???H???Cl????????????CF 3?Me???Cl???H???F?????????????CF 3?Me???Cl???H???Me????????????SMe ?Me???Cl???H???Me????????????OMe ?Me???Cl???H???Me????????????OEt ?Me???Cl???H???Me????????????n-C 3F 7?Me???Cl???H???Me????????????i-C 3F 7?Me???Cl???H???Me????????????Et ?Me???Cl???H???Me????????????OCF 2CHF 2?Me???Cl???H???Me????????????SCF 2CHF 2?Me???Cl???H???Me????????????SO 2Me ?Me???Cl???H???3-Me-2-???????CF 3Pyridyl Me Cl H CF 3??????????CF 3?Me???Cl???H???CF 3??????????Me ?Me???Cl???H???OMe???????????CF 3?Me???Cl???H???H?????????????CF 3?Me???Cl???H???H?????????????OCHF 2?Me???Cl???H???H?????????????C 2F 5 | R 3?? R 4a? R 4b? R 5a?????????? R 5b?Me????Cl????H????H??????????????n-C 3F 7?Me????Cl????H????H??????????????i-C 3F 7?Me????Cl????H????H??????????????Br ?Me????Cl????H????H??????????????Cl ?Me????Cl????H????H??????????????SCF 3?Me????Cl????H????Ph?????????????CF 3Me Cl H Ph Cl Me Cl H Ph Br Me Cl H 2-pyridyl CF 3Me Cl H 2-pyridyl Cl Me Cl H 2-ClPh CF 3?Me????Cl????H????2-ClPh?????????OCF 3?Me????Cl????H????2-ClPh?????????Br ?Me????Cl????H????2-ClPh?????????Cl ?Me????Cl????H????2-ClPh?????????SCHF 2?Me????Cl????H????2-BrPh?????????CF 3?Me????Cl????H????2-MePh?????????CF 3?Me????Cl????H????2-CNPh?????????CF 3Me?????Cl????H????2-FPh??????????CF 3?Me????Cl????H????2,6-F 2Ph??????CF 3?Me????Cl????H????2,4-F 2Ph??????CF 3?Me????Cl????H????2,5-F 2Ph??????CF 3?Me????Cl????H????2-MeOPh????????CF 3Me Cl H 3-Cl-2-pyridyl CF 3Me Cl H 3-Cl-2-pyridyl OCF 3Me Cl H 3-Cl-2-pyridyl Br Me Cl H 3-Cl-2-pyridyl Cl Me Cl H 3-Cl-2-pyridyl SCHF 2Me Cl H 3-F-2-pyridyl CF 3?Me????Cl????H????3-CF 3-2-??????CF 3Pyridyl Me Cl H Me SO 2CF 3Me Cl H 3-Br-2-pyridyl CF 3Me Cl H 3-Br-2-pyridyl OCF 3Me Cl H 3-Br-2-pyridyl Br Me Cl H 3-Br-2-pyridyl Cl Et Cl H H C 2F 5 |
Table 8
| R 3?? R 4a? R 4b? R 5a? R 5b?Me????H????Me????H?????CF 3?Me????H????Me????H?????OCF 3?Et????H????Me????H?????OCF 3?Me????H????Me????Me????Br ?Me????H????Me????Et????Br ?Me????H????Me????Me????Cl ?Me????H????Me????Et????Cl ?Me????H????Me????Me????I ?Me????H????Me????Me????CF 3?Me????H????Me????Me????OCF 3?Et????H????Me????Me????CF 3?Me????H????Me????Me????SCF 3?Me????H????Me????Me????SCHF 2?Me????H????Me????Me????OCHF 2?n-Pr??H????Me????Me????CF 3?Me????H????Me????Me????C 2F 5?Et????H????Me????Me????C 2F 5?Me????H????Me????Et????CF 3?Me????H????Me????n-Pr??CF 3?Me????H????Me????i-Pr??CF 3?Me????H????Me????Cl????CF 3?Me????H????Me????F?????CF 3?Me????H????Me????Me????SMe ?Me????H????Me????Me????OMe ?Me????H????Me????Me????OEt ?Me????H????Me????Me????n-C 3F 7?Me????H????Me????Me????i-C 3F 7?Me????H????Me????Me????Et | R 3?? R 4a? R 4b R 5a?? R 5b?Me????H????H????H?????CF 3?Me????H????H????H?????CCF 3?Et????H????H????H?????OCF 3?Me????H????H????Me????Br ?Me????H????H????Et????Br ?Me????H????H????Me????Cl ?Me????H????H????Et????Cl ?Me????H????H????Me????I ?Me????H????H????Me????CF 3?Me????H????H????Me????OCF 3?Et????H????H????Me????CF 3?Me????H????H????Me????SCF 3?Me????H????H????Me????SCHF 2?Me????H????H????Me????OCHF 2?n-Pr??H????H????Me????CF 3?Me????H????H????Me????C 2F 5?Et????H????H????Me????C 2F 5?Me????H????H????Et????CF 3?Me????H????H????n-Pr??CF 3?Me????H????H????i-Pr??CF 3?Me????H????H????Cl????CF 3?Me????H????H????F?????CF 3?Me????H????H????Me????SMe ?Me????H????H????Me????OMe ?Me????H????H????Me????OEt ?Me????H????H????Me????n-C 3F 7?Me????H????H????Me????i-C 3F 7?Me????H????H????Me????Et |
| ? R 3?? R 4a R 4b? R 5a???????? R 5b??Me????H????Me????Me??????????OCF 2CHF 2??Me????H????Me????Me??????????SCF 2CHF 2??Me????H????Me????Me??????????SO 2Me ??Me????H????Me????Me??????????SO 2CF 3??Me????H????Me????CF 3????????CF 3??Me????H????Me????CF 3????????Me ??Me????H????Me????OMe?????????CF 3??Me????H????Me????H???????????CF 3??Me????H????Me????H???????????OCHF 2??Me????H????Me????H???????????C 2F 5??Et????H????Me????H???????????C 2F 5??Me????H????Me????H???????????OCF 3??Me????H????Me????H???????????OCF 2CHF 2??Me????H????Me????H???????????SCF 2CHF 2??Me????H????Me????H???????????n-C 3F 7??Me????H????Me????H???????????i-C 3F 7??Me????H????Me????H???????????Br ??Me????H????Me????H???????????Cl ??Me????H????Me????H???????????SCF 3??Me????H????Me????Ph??????????CF 3Me H Me Ph Cl Me H Me Ph Br Me H Me 2-pyridyl CF 3Me H Me 2-pyridyl Cl Me H Me 2-ClPh CF 3??Me????H????Me????2-ClPh??????OCF 3??Me????H????Me????2-ClPh??????Br ??Me????H????Me????2-ClPh??????Cl ??Me????H????Me????2-ClPh??????SCHF 2??Me????H????Me????2-BrPh??????CF 3??Me????H????Me????2-MePh??????CF 3??Me????H????Me????2-CNPh??????CF 3??Me????H????Me????2-FPh???????CF 3??Me????H????Me????2,6-F 2Ph???CF 3??Me????H????Me????2,4-F 2Ph???CF 3??Me????H????Me????2,5-F 2Ph???CF 3??Me????H????Me????2-MeOPh?????CF 3 | R 3?? R 4a? R 4b R 5a???????? R 5b?Me????H????H????Me??????????OCF 2CHF 2?Me????H????H????Me??????????SCF 2CHF 2?Me????H????H????Me??????????SO 2Me ?Me????H????H????Me??????????SO 2CF 3?Me????H????H????CF 3????????CF 3?Me????H????H????CF 3????????Me ?Me????H????H????OMe?????????CF 3?Me????H????H????H???????????CF 3?Me????H????H????H???????????OCHF 2?Me????H????H????H???????????C 2F 5?Et????H????H????H???????????C 2F 5?Me????H????H????H???????????OCF 3?Me????H????H????H???????????OCF 2CHF 2?Me????H????H????H???????????SCF 2CHF 2?Me????H????H????H???????????n-C 3F 7?Me????H????H????H???????????i-C 3F 7?Me????H????H????H???????????Br ?Me????H????H????H???????????Cl ?Me????H????H????H???????????SCF 3?Me????H????H????Ph??????????CF 3Me H H Ph Cl Me H H Ph Br Me H H 2-pyridyl CF 3Me H H 2-pyridyl Cl Me H H 2-ClPh CF 3?Me????H????H????2-ClPh??????OCF 3?Me????H????H????2-ClPh??????Br ?Me????H????H????2-ClPh??????Cl ?Me????H????H????2-ClPh??????SCHF 2?Me????H????H????2-BrPh??????CF 3?Me????H????H????2-MePh??????CF 3?Me????H????H????2-CNPh??????CF 3?Me????H????H????2-FPh???????CF 3?Me????H????H????2,6-F 2Ph???CF 3?Me????H????H????2,4-F 2Ph???CF 3?Me????H????H????2,5-F 2Ph???CF 3?Me????H????H????2-MeOPh?????CF 3 |
| R 3?? R 4a? R 4b??? R 5a???????? R 5bMe H Me 3-Cl-2-pyridyl CF 3Me H Me 3-Cl-2-pyridyl OCF 3Me H Me 3-Cl-2-pyridyl Br Me H Me 3-Cl-2-pyridyl Cl Me H Me 3-Cl-2-pyridyl SCHF 2Me H Me 3-F-2-pyridyl CF 3?Me????H????Me????3-CF 3-2-??????CF 3Pyridyl Me H Me 3-Me-2-CF 3Pyridyl Me H Me 3-Br-2-pyridyl CF 3Me H Me 3-Br-2-pyridyl OCF 3Me H Me 3-Br-2-pyridyl Br Me H Me 3-Br-2-pyridyl Cl Me Me H H CF 3?Me????Me???H?????H??????????????OCF 3?Et????Me???H?????H??????????????OCF 3?Me????Me???H?????Me?????????????Br ?Me????Me???H?????Et?????????????Br ?Me????Me???H?????Me?????????????Cl ?Me????Me???H?????Et?????????????Cl ?Me????Me???H?????Me?????????????I ?Me????Me???H?????Me?????????????CF 3?Me????Me???H?????Me?????????????OCF 3?Et????Me???H?????Me?????????????CF 3?Me????Me???H?????Me?????????????SCF 3?Me????Me???H?????Me?????????????SCHF 2?Me????Me???H?????Me?????????????OCHF 2?n-Pr??Me???H?????Me?????????????CF 3?Me????Me???H?????Me?????????????C 2F 5?Et????Me???H?????Me?????????????C 2F 5?Me????Me???H?????Et?????????????CF 3?Me????Me???H?????n-Pr???????????CF 3?Me????Me???H?????i-Pr???????????CF 3?Me????Me???H?????Cl?????????????CF 3?Me????Me???H?????F??????????????CF 3?Me????Me???H?????Me?????????????SMe | R 3?? R 4a? R 4b???? R 5a???????? R 5bMe H H 3-Cl-2-pyridyl CF 3Me H H 3-Cl-2-pyridyl OCF 3Me H H 3-Cl-2-pyridyl Br Me H H 3-Cl-2-pyridyl Cl Me H H 3-Cl-2-pyridyl SCHF 2Me H H 3-F-2-pyridyl CF 3?Me????H????H????3-CF 3-2-????????CF 3Pyridyl Me H H 3-Me-2-CF 3Pyridyl Me H H 3-Br-2-pyridyl CF 3Me H H 3-Br-2-pyridyl OCF 3Me H H 3-Br-2-pyridine radicals Br Me H H 3-Br-2-pyridine radicals Cl Me H Cl Et Br Me H Cl Me Cl Me H Cl Et Cl Me H Cl Me I Me H Cl Me CF3?Me????H????Cl???Me???????????????OF 3?Et????H????Cl???Me???????????????CF 3?Me????H????Cl???Me???????????????SCF 3?Me????H????Cl???Me???????????????SCHF 2?Me????H????Cl???Me???????????????OCHF 2?n-Pr??H????Cl???Me???????????????CF 3?Me????H????Cl???Me???????????????C 2F 5?Et????H????Cl???Me???????????????C 2F 5?Me????H????Cl???Et???????????????CF 3?Me????H????Cl???n-Pr?????????????CF 3?Me????H????Cl???i-Pr?????????????CF 3?Me????H????Cl???Cl???????????????CF 3?Me????H????Cl???F????????????????CF 3?Me????H????Cl???Me???????????????SMe ?Me????H????Cl???Me???????????????OMe ?Me????H????Cl???Me???????????????OEt ?Me????H????Cl???Me???????????????n-C 3F 7?Me????H????Cl???Me???????????????i-C 3F 7 |
| ??? R 3 R 4a? R 4b? R 5a???? R 5b????Me??Me????H????Me???????OMe ????Me??Me????H????Me???????OEt ????Me??Me????H????Me???????n-C 3F 7????Me??Me????H????Me???????i-C 3F 7????Me??Me????H????Me???????Et ????Me??Me????H????Me???????OCF 2CHF 2????Me??Me????H????Me???????SCF 2CHF 2????Me??Me????H????Me???????SO 2Me ????Me??Me????H????Me???????SO 2CF 3????Me??Me????H????CF 3?????CF 3????Me??Me????H????CF 3?????Me ????Me??Me????H????OMe??????CF 3????Me??Me????H????H????????CF 3????Me??Me????H????H????????OCHF 2????Me??Me????H????H????????C 2F 5????Et??Me????H????H????????C 2F 5????Me??Me????H????H????????OCF 3????Me??Me????H????H????????OCF 2CHF 2????Me??Me????H????H????????SCF 2CHF 2????Me??Me????H????H????????n-C 3F 7????Me??Me????H????H????????i-C 3F 7????Me??Me????H????H????????Br ????Me??Me????H????H????????Cl ????Me??Me????H????H????????SCF 3????Me??Me????H????Ph???????CF 3Me Me H Ph Cl Me Me H Ph Br Me Me H 2-pyridyl CF 3Me Me H 2-pyridyl Cl Me Me H 2-ClPh CF 3????Me??Me????H????2-ClPh???OCF 3????Me??Me????H????2-ClPh???Br ????Me??Me????H????2-ClPh???Cl ????Me??Me????H????2-ClPh???SCHF 2????Me??Me????H????2-BrPh???CF 3????Me??Me????H????2-MePh???CF 3????Me??Me????H????2-CNPh???CF 3 | R 3?? R 4a? R 4b? R 5a????? R 5b?Me????H????Cl????Me????????El ?Me????H????Cl????Me????????OCF 2CHF 2?Me????H????Cl????Me????????SCF 2CHF 2?Me????H????Cl????Me????????SO 2Me ?Me????H????Cl????Me????????SO 2CF 3?Me????H????Cl????CF 3??????CF 3?Me????H????Cl????CF 3??????Me ?Me????H????Cl????OMe???????CF 3?Me????H????Cl????H?????????CF 3?Me????H????Cl????H?????????OCHF 2?Me????H????Cl????H?????????C 2F 5?Et????H????Cl????H?????????C 2F 5?Me????H????Cl????H?????????OCF 3?Me????H????Cl????H?????????OCF 2CHF 2?Me????H????Cl????H?????????SCF 2CHF 2?Me????H????Cl????H?????????n-C 3F 7?Me????H????Cl????H?????????i-C 3F 7?Me????H????Cl????H?????????Br ?Me????H????Cl????H?????????Cl ?Me????H????Cl????H?????????SCF 3?Me????H????Cl????Ph????????CF 3Me H Cl Ph Cl Me H Cl Ph Br Me H Cl 2-pyridyl CF 3Me H Cl 2-pyridyl Cl Me H Cl 2-ClPh CF 3?Me????H????Cl????2-ClPh????OCF 3?Me????H????Cl????2-ClPh????Br ?Me????H????Cl????2-ClPh????Cl ?Me????H????Cl????2-ClPh????SCHF 2?Me????H????Cl????2-BrPh????CF 3?Me????H????Cl????2-MePh????CF 3?Me????H????Cl????2-CNPh????CF 3?Me????H????Cl????2-FPh?????CF 3?Me????H????Cl????2,6-F 2Ph?CF 3?Me????H????Cl????2,4-F 2Ph?CF 3?Me????H????Cl????2,5-F 2Ph?CF 3 |
| ? R 3? R 4a? R 4b? R 5a????????? R 5b??Me???Me????H????2-FPh??????????CF 3??Me???Me????H????2,6-F 2Ph??????CF 3??Me???Me????H????2,4-F 2Ph??????CF 3??Me???Me????H????2,5-F 2Ph??????CF 3??Me???Me????H????2-MeOPh????????CF 3Me Me H 3-Cl-2-pyridyl CF 3Me Me H 3-Cl-2-pyridyl OCF 3??Me???Me????H????3-CF 3-2-??????CF 3Pyridyl Me Me H 3-Me-2-CF 3Pyridyl Me Me H 3-Cl-2-pyridyl SCHF 2Me Me H 3-F-2-pyridyl CF 3Me Me H 3-Cl-2-pyridyl Br Me Me H 3-Cl-2-pyridyl Cl Me Me H 3-Br-2-pyridyl CF 3Me Me H 3-Br-2-pyridyl OCF 3Me Me H 3-Br-2-pyridine radicals Br Me Me H 3-Br-2-pyridine radicals Cl Me Cl H Me Br Me Cl H Et Br Me Cl H Me Cl Me Cl H Et Cl Me Cl H Me I Me Cl H Me CF3??Me???Cl????H????Me?????????????OCF 3??Et???Cl????H????Me?????????????CF 3??Me???Cl????H????Me?????????????SCF 3??Me???Cl????H????Me?????????????SCHF 2??Me???Cl????H????Me?????????????OCHF 2??n-Pr?Cl????H????Me?????????????CF 3??Me???Cl????H????Me?????????????C 2F 5??Et???Cl????H????Me?????????????C 2F 5??Me???Cl????H????Et?????????????CF 3??Me???Cl????H????n-Pr???????????CF 3??Me???Cl????H????i-Pr???????????CF 3??Me???Cl????H????Cl?????????????CF 3 | R 3?? R 4a? R 4b? R 5a??????????? R 5b?Me????H?????Cl???2-MeOPh??????????CF 3Me H Cl 3-Cl-2-pyridyl CF 3Me H Cl 3-Cl-2-pyridyl OCF3 Me H Cl 3-Cl-2-pyridyl Br Me H Cl 3-Cl-2-pyridyl Cl Me H Cl 3-Cl-2-pyridyl SCHF 2Me H Cl 3-F-2-pyridyl CF 3?Me????H?????Cl???3-CF 3-2-????????CF 3Pyridyl Me H Cl 3-Me-2-CF 3Pyridyl Me H Cl 3-Br-2-pyridyl CF 3Me H Cl 3-Br-2-pyridyl OCF 3Me H Cl 3-Br-2-pyridyl Br Me H Cl 3-Br-2-pyridyl Cl Me Cl H H OCF 3?Me????Cl????H????H????????????????OCF 2CHF 2?Me????Cl????H????H????????????????SCF 2CHF 2?Me????Cl????H????H????????????????n-C 3F 7?Me????Cl????H????H????????????????i-C 3F 7?Me????Cl????H????H????????????????Br ?Me????Cl????H????H????????????????Cl ?Me????Cl????H????H????????????????SCF 3?Me????Cl????H????Ph???????????????CF 3Me Cl H Ph Cl Me Cl H Ph Br Me Cl H 2-pyridyl CF 3Me Cl H 2-pyridyl Cl Me Cl H 2-ClPh CF 3?Me????Cl????H????2-ClPh???????????OCF 3?Me????Cl????H????2-ClPh???????????Br ?Me????Cl????H????2-ClPh???????????Cl ?Me????Cl????H????2-ClPh???????????SCHF 2?Me????Cl????H????2-BrPh???????????CF 3?Me????Cl????H????2-MePh???????????CF 3?Me????Cl????H????2-CNPh???????????CF 3?Me????Cl????H????2-FPh????????????CF 3 |
| R 3?? R 4a? R 4b R 5a????? R 5bMe????Cl????H????F?????????CF 3Me????Cl????H????Me????????SMe Me????Cl????H????Me????????OMe Me????Cl????H????Me????????OEt Me????Cl????H????Me????????n-C 3F 7Me????Cl????H????Me????????i-C 3F 7Me????Cl????H????Me????????Et Me????Cl????H????Me????????OCF 2CHF 2Me????Cl????H????Me????????SCF 2CHF 2Me????Cl????H????Me????????SO 2Me Me????Cl????H????Me????????SO 2CF 3Me????Cl????H????3-CF 3-2-?CF 3Pyridyl Me Cl H CF 3??????Me Me????Cl????H????OMe???????CF 3Me????Cl????H????H?????????CF 3Me????Cl????H????H?????????OCHF 2Me????Cl????H????H?????????C 2F 5 | R 3?? R 4a? R 4b???? R 5a??????? R 5b?Me????Cl????H????2,6-F 2Ph??????CF 3?Me????Cl????H????2,4-F 2Ph??????CF 3?Me????Cl????H????2,5-F 2Ph??????CF 3?Me????Cl????H????2-MeOPh????????CF 3Me Cl H 3-Cl-2-pyridyl CF 3Me Cl H 3-Cl-2-pyridyl OCF 3Me Cl H 3-Cl-2-pyridyl Br Me Cl H 3-Cl-2-pyridyl Cl Me Cl H 3-Cl-2-pyridyl SCHF 2Me Cl H 3-F-2-pyridyl CF 3?Me????Cl????H????CF 3???????????CF 3?Me????Cl????H????3-Me-2-????????CF 3Pyridyl Me Cl H 3-Br-2-pyridyl CF 3Me Cl H 3-Br-2-pyridyl OCF 3Me Cl H 3-Br-2-pyridyl Br Me Cl H 3-Br-2-pyridyl Cl Et Cl H H C 2F 5 |
Table 9
| R 3? R 4a? R 4b? R 5a? R 5b?Me????H????Me????H????CF 3?Me????H????Me????H????OCF 3?Et????H????Me????H????OCF 3?Me????H????Me????Me???Br ?Me????H????Me????Et???Br ?Me????H????Me????Me???Cl ?Me????H????Me????Et???Cl ?Me????H????Me????Me???I ?Me????H????Me????Me???CF 3 | R 3? R 4a? R 4b? R 5a? R 5b?Me????H????H????H?????CF 3?Me????H????H????H?????OCF 3?Et????H????H????H?????OCF 3?Me????H????H????Me????Br ?Me????H????H????Et????Br ?Me????H????H????Me????Cl ?Me????H????H????Et????Cl ?Me????H????H????Me????I ?Me????H????H????Me????CF 3 |
| ? R 3? R 4a? R 4b? R 5a????? R 5b??Me????H????Me????Me????????OCF 3??Et????H????Me????Me????????CF 3??Me????H????Me????Me????????SCF 3??Me????H????Me????Me????????SCHF 2??Me????H????Me????Me????????OCHF 2??n-Pr??H????Me????Me????????CF 3??Me????H????Me????Me????????C 2F 5??Et????H????Me????Me????????C 2F 5??Me????H????Me????Et????????CF 3??Me????H????Me????n-Pr??????CF 3??Me????H????Me????i-Pr??????CF 3??Me????H????Me????i-Pr??????OCF 3??Me????H????Me????Me????????SMe ??Me????H????Me????Me????????OMe ??Me????H????Me????Me????????OEt ??Me????H????Me????Me????????n-C 3F 7??Me????H????Me????Me????????i-C 3F 7??Me????H????Me????Me????????Et ??Me????H????Me????Me????????OCF 2CHF 2??Me????H????Me????Me????????SCF 2CHF 2??Me????H????Me????Me????????SO 2Me ??Me????H????Me????Me????????SO 2CF 3??Me????H????Me????CHF 2?????CF 3??Me????H????Me????CHF 2?????Me ??Me????H????Me????Ph????????CF 3Me H Me Ph Cl Me H Me Ph Br Me H Me 2-pyridyl CF 3Me H Me 2-pyridyl Cl Me H Me 2-ClPh CF 3??Me????H????Me????2-ClPh????OCF 3??Me????H????Me????2-ClPh????Br ??Me????H????Me????2-ClPh????Cl ??Me????H????Me????2-ClPh????SCHF 2??Me????H????Me????2-BrPh????CF 3??Me????H????Me????2-MePh????CF 3??Me????H????Me????2-CNPh????CF 3 | ? R 3? R 4a? R 4b R 5a????? R 5b??Me????H????H????Me????????OCF 3??Et????H????H????Me????????CF 3??Me????H????H????Me????????SCF 3??Me????H????H????Me????????SCHF 2??Me????H????H????Me????????OCHF 2??n-Pr??H????H????Me????????CF 3??Me????H????H????Me????????C 2F 5??Et????H????H????Me????????C 2F 5??Me????H????H????Et????????CF 3??Me????H????H????n-Pt??????CF 3??Me????H????H????i-Pr??????CF 3??Me????H????H????Me????????SMe ??Me????H????H????Me????????OMe ??Me????H????H????Me????????OEt ??Me????H????H????Me????????n-C 3F 7??Me????H????H????Me????????i-C 3F 7??Me????H????H????Me????????Et ??Me????H????H????Me????????OCF 2CHF 2??Me????H????H????Me????????SCF 2CHF 2??Me????H????H????Me????????SO 2Me ??Me????H????H????Me????????SO 2CF 3??Me????H????H????CF 3??????CF 3??Me????H????H????CF 3??????Me ??Me????H????H????Ph????????CF 3Me H H Ph Cl Me H H Ph Br Me H H 2-pyridyl CF 3Me H H 2-pyridyl Cl Me H H 2-ClPh CF 3??Me????H????H????2-ClPh????OCF 3??Me????H????H????2-ClPh????Br ??Me????H????H????2-ClPh????Cl ??Me????H????H????2-ClPh????SCHF 2??Me????H????H????2-BrPh????CF 3??Me????H????H????2-MePh????CF 3??Me????H????H????2-CNPh????CF 3??Me????H????H????2-FPh?????CF 3 |
| ? R 3?? R 4a R 4b??? R 5a????????? R 5b??Me????H????Me????2-FPh??????????CF 3??Me????H????Me????2,6-F 2Ph??????CF 3??Me????H????Me????2,4-F 2Ph??????CF 3??Me????H????Me????2,5-F 2Ph??????CF 3??Me????H????Me????2-MeOPh????????CF 3Me H Me 3-Cl-2-pyridyl CF 3Me H Me 3-Cl-2-pyridyl OCF 3Me H Me 3-Cl-2-pyridyl Br Me H Me 3-Cl-2-pyridyl Cl Me H Me 3-Cl-2-pyridyl SCHF 2??Me????H????Me????3-CF 3-2-??????CF 3Pyridyl Me H Me 3-Me-2-CF 3Pyridyl Me H Me 3-F-2-pyridyl CF 3Me H Me 3-Br-2-pyridyl CF 3Me H Me 3-Br-2-pyridyl OCF 3Me H Me 3-Br-2-pyridine radicals Br Me H Me 3-Br-2-pyridine radicals Cl Me Me H Me Br Me Me H Et Br Me Me H Me Cl Me Me H Et Cl Me Me H Me I Me Me H Me CF3??Me????Me???H?????Me?????????????OCF 3??Et????Me???H?????Me?????????????CF 3??Me????Me???H?????Me?????????????SCF 3??Me????Me???H?????Me?????????????SCHF 2??Me????Me???H?????Me?????????????OCHF 2??n-Pr??Me???H?????Me?????????????CF 3??Me????Me???H?????Me?????????????C 2F 5??Et????Me???H?????Me?????????????C 2F 5??Me????Me???H?????Et?????????????CF 3??Me????Me???H?????n-Pr???????????CF 3??Me????Me???H?????i-Pr???????????CF 3??Me????Me???H?????Me?????????????SMe | R 3?? R 4a? R 4b???? R 5a??????? R 5b?Me????H????H?????2,6-F 2Ph??????CF 3?Me????H????H?????2,4-F 2Ph??????CF 3?Me????H????H?????2,5-F 2Ph??????CF 3?Me????H????H?????2-MeOPh????????CF 3Me H H 3-Cl-2-pyridyl CF 3Me H H 3-Cl-2-pyridyl OCF 3Me H H 3-Cl-2-pyridyl Br Me H H 3-Cl-2-pyridyl Cl Me H H 3-Cl-2-pyridyl SCHF 2Me H H 3-F-2-pyridyl CF 3?Me????H????H?????3-CF 3-2-??????CF 3Pyridyl Me H H 3-Me-2-CF 3Pyridyl Me H H 3-B-r2-pyridyl CF 3Me H H 3-Br-2-pyridyl OCF 3Me H H 3-Br-2-pyridine radicals Br Me H H 3-Br-2-pyridine radicals Cl Me H Cl Et Br Me H Cl Me Cl Me H Cl Et Cl Me H Cl Me I Me H Cl Me CF3?Me????H????Cl????Me?????????????OCF 3?Et????H????Cl????Me?????????????CF 3?Me????H????Cl????Me?????????????SCF 3?Me????H????Cl????Me?????????????SCHF 2?Me????H????Cl????Me?????????????OCHF 2?n-Pr??H????Cl????Me?????????????CF 3?Me????H????Cl????Me?????????????C 2F 5?Et????H????Cl????Me?????????????C 2F 5?Me????H????Cl????Et?????????????CF 3?Me????H????Cl????n-Pr???????????CF 3?Me????H????Cl????i-Pr???????????CF 3?Me????H????Cl????Me?????????????SMe ?Me????H????Cl????Me?????????????OMe ?Me????H????Cl????Me?????????????CEt |
| R 3? R 4a? R 4b R 5a???????????? R 5b?Me??Me????H????Me??????????????OMe ?Me??Me????H????Me??????????????OEt ?Me??Me????H????Me??????????????n-C 3F 7?Me??Me????H????Me??????????????i-C 3F 7?Me??Me????H????Me??????????????Et ?Me??Me????H????Me??????????????OCF 2CHF 2?Me??Me????H????Me??????????????SCF 2CHF 2?Me??Me????H????Me??????????????SO 2Me ?Me??Me????H????Me??????????????SO 2CF 3?Me??Me????H????CF 3????????????CF 3?Me??Me????H????CF 3????????????Me ?Me??Me????H????Ph??????????????CF 3Me Me H Ph Cl Me Me H Ph Br Me Me H 2-pyridyl CF 3Me Me H 2-pyridyl Cl Me Me H 2-ClPh CF 3?Me??Me????H????2-ClPh??????????OCF 3?Me??Me????H????2-ClPh??????????Br ?Me??Me????H????2-ClPh??????????Cl ?Me??Me????H????2-ClPh??????????SCHF 2?Me??Me????H????2-BrPh??????????CF 3?Me??Me????H????2-MePh??????????CF 3?Me??Me????H????2-CNPh??????????CF 3?Me??Me????H????2-FPh???????????CF 3?Me??Me????H????2,6-F 2Ph???????CF 3?Me??Me????H????2,4-F 2Ph???????CF 3?Me??Me????H????2,5-F 2Ph???????CF 3?Me??Me????H????2-MeOPh?????????CF 3Me Me H 3-Cl-2-pyridyl CF 3Me Me H 3-Cl-2-pyridyl OCF 3Me Me H 3-Cl-2-pyridyl Br Me Me H 3-Cl-2-pyridyl Cl Me Me H 3-CF 3-2-???????CF 3Pyridyl Me Me H 3-Me-2-CF 3Pyridyl | R 3??? R 4a R 4b? R 5a??????????? R 5b?Me????H????Cl????Me?????????????r-C 3F 7?Me????H????Cl????Me?????????????i-C 3F 7?Me????H????Cl????Me?????????????Et ?Me????H????Cl????Me?????????????OCF 2CHF 2?Me????H????Cl????Me?????????????SCF 2CHF 2?Me????H????Cl????Me?????????????SO 2Me ?Me????H????Cl????Me?????????????SO 2CF 3?Me????H????Cl????CF 3???????????CF 3?Me????H????Cl????CF 3???????????Me ?Me????H????Cl????Ph?????????????CF 3Me H Cl Ph Cl Me H Cl Ph Br Me H Cl 2-pyridyl CF 3Me H Cl 2-pyridyl Cl Me H Cl 2-ClPh CF 3?Me????H????Cl????2-ClPh?????????OCF 3?Me????H????Cl????2-ClPh?????????Br ?Me????H????Cl????2-ClPh?????????Cl ?Me????H????Cl????2-ClPh?????????SCHF 2?Me????H????Cl????2-BrPh?????????CF 3?Me????H????Cl????2-MePh?????????CF 3?Me????H????Cl????2-CNPh?????????CF 3?Me????H????Cl????2-FPh??????????CF 3?Me????H????Cl????2,6-F 2Ph??????CF 3?Me????H????Cl????2,4-F 2Ph??????CF 3?Me????H????Cl????2,5-F 2Ph??????CF 3?Me????H????Cl????2-OMe??????????CF 3Me H Cl 3-Cl-2-pyridyl CF 3Me H Cl 3-Cl-2-pyridyl OCF 3Me H Cl 3-Cl-2-pyridyl Br Me H Cl 3-Cl-2-pyridyl Cl Me H Cl 3-Cl-2-pyridyl SCHF 2Me H Cl 3-F-2-pyridyl CF 3?Me????H????Cl????3-CF 3-2-??????CF 3Pyridyl Me H Cl 3-Me-2-CF 3Pyridyl |
| R 3? R 4a? R 4b??? R 5a????????? R 5bMe Me H 3-Cl-2-pyridyl SCHF 2Me Me H 3-F-2-pyridyl CF 3Me Me H 3-Br2-pyridyl CF 3Me Me H 3-Br-2-pyridyl OCF 3Me Me H 3-Br-2-pyridine radicals Br Me Me H 3-Br-2-pyridine radicals Cl Me Cl H Me Br Me Cl H Et Br Me Cl H Me Cl Me Cl H Et Cl Me Cl H Me I Me Cl H Me CF3?Me???Cl????H????Me??????????????OCF 3?Et???Cl????H????Me??????????????CF 3?Me???Cl????H????Me??????????????SCF 3?Me???Cl????H????Me??????????????SCHF 2?Me???Cl????H????Me??????????????OCHF 2?n-Pr?Cl????H????Me??????????????CF 3?Me???Cl????H????Me??????????????C 2F 5?Et???Cl????H????Me??????????????C 2F 5Me Cl H 3-Cl-2-pyridyl CF 3Me Cl H 3-Cl-2-pyridyl OCF 3Me Cl H 3-Cl-2-pyridyl Br Me Cl H 3-Cl-2-pyridyl Cl Me Cl H 3-Cl-2-pyridyl SCHF 2Me Cl H 3-F-2-pyridyl CF 3?Me???Cl????H????3-CF 3-2-???????CF 3Pyridyl Me Cl H 3-Br-2-pyridyl CF 3Me Cl H 3-Br-2-pyridyl OCF 3Me Cl H 3-Br-2-pyridyl Br Me Cl H 3-Br-2-pyridyl Cl Me Cl H 2,4-F 2Ph???????CF 3?Me???Cl????H????2,5-F 2Ph???????CF 3?Me???Cl????H????2-OMe???????????CF 3?Me???Cl????H????2-ClPh??????????OCF 3 | R 3? R 4a? R 4b???? R 5a?????? R 5bMe H Cl 3-Br-2-pyridyl CF 3Me H Cl 3-Br-2-pyridyl OCF 3Me H Cl 3-Br-2-pyridyl Br Me H Cl 3-Br-2-pyridyl Cl Me Cl H Et CF 3?Me???Cl????H????n-Pr???????????CF 3?Me???Cl????H????i-Pr???????????CF 3?Me???Cl????H????Me?????????????SMe ?Me???Cl????H????Me?????????????CMe ?Me???Cl????H????Me?????????????OEt ?Me???Cl????H????Me?????????????n-C 3F 7?Me???Cl????H????Me?????????????i-C 3F 7?Me???Cl????H????Me?????????????Et ?Me???Cl????H????Me?????????????OCF 2CHF 2?Me???Cl????H????Me?????????????SCF 2CHF 2?Me???Cl????H????Me?????????????SO 2Me ?Me???Cl????H????Me?????????????SO 2CF 3?Me???Cl????H????CF 3???????????CF 3?Me???Cl????H????CF 3???????????Me ?Me???Cl????H????OMe????????????CF 3?Me???Cl????H????Ph?????????????CF 3Me Cl H Ph Cl Me Cl H Ph Br Me Cl H 2-pyridyl CF 3Me Cl H 2-pyridyl Cl Me Cl H 2-ClPh CF 3?Me???Cl????H????3-Me-2-????????CF 3Pyridyl Me Cl H 2-ClPh Br Me Cl H 2-ClPh Cl Me Cl H 2-ClPh SCHF 2?Me???Cl????H????2-BrPh?????????CF 3?Me???Cl????H????2-MePh?????????CF 3?Me???Cl????H????2-CNPh?????????CF 3?Me???Cl????H????2-FPh??????????CF 3?Me???Cl????H????2,6-F 2Ph??????CF 3 |
Table 10
Preparaton/effectiveness
| R 3??? R 4a R 4b? R 5a?? R 5b?Me????H????Me????H?????CHF 2?Me????H????Me????H?????CH 2CF 3?Et????H????Me????H?????CH 2CF 3?Me????H????Me????Me????CH 2CF 3?Me????H????Me????Et????CH 2CF 3?Me????H????Me????Me????CF 2CHF 2?Me????H????Me????Et????CHF 2?Me????H????Me????Me????CHF 2?Me????H????Me????Me????CBrF 2?Me????H????Me????Me????CHF 2?Et????H????Me????Me????CH 2CF 3?Me????H????Me????Me????Et ?Me????H????Me????M?????n-Pr ?Me????H????Me????Me????CH 2C 2F 5?n-Pr??H????Me????Me????CH 2CF 3?Me????H????Me????Me????CF 3?Et????H????Me????Me????C 2F 5?Me????H????Me????Et????CHF 2?Me????H????Me????n-Pr??CH 2CF 3?Me????H????Me????i-Pr??CHF 2?Me????H????Me????Cl????CH 2CF 3?Me????H????Me????F?????CH 2CF 3?Me????H????Me????Me????CH 2Cl ?Me????H????Me????Me????CClF 2?Me????H????Me????Me????CH 2CH 2Cl ?Me????H????Me????Me????n-C 3F 7?Me????H????Me????Me????i-C 3F 7?Me????H????Me????Me????Allyl | R 3?? R 4a? R 4b R 5a?? R 5b?Me????H????H????H?????CHF 2?Me????H????H????H?????CH 2CF 3?Et????H????H????H?????CH 2CF 3?Me????H????H????Me????CH 2CF 3?Me????H????H????Et????CH 2CF 3?Me????H????H????Me????CF 2CHF 2?Me????H????H????Et????CHF 2?Me????H????H????Me????CHF 2?Me????H????H????Me????CBrF 2?Me????H????H????Me????CHF 2?Et????H????H????Me????CH 2CF 3?Me????H????H????Me????Et ?Me????H????H????Me????n-Pr ?Me????H????H????Me????CH 2C 2F 5?n-Pr??H????H????Me????CH 2CF 3?Me????H????H????Me????CF 3?Et????H????H????Me????C 2F 5?Me????H????H????Et????CHF 2?Me????H????H????n-Pr??CH 2CF 3?Me????H????H????i-Pr??CHF 2?Me????H????H????Cl????CH 2CF 3?Me????H????H????F?????CH 2CF 3?Me????H????H????Me????CH 2Cl ?Me????H????H????Me????CClF 2?Me????H????H????Me????CH 2CH 2Cl ?Me????H????H????Me????n-C 3F 7?Me????H????H????Me????i-C 3F 7?Me????H????H????Me????Allyl |
| R 3?? R 4a? R 4b? R 5a???????????? R 5b?Me????H????Me????Et?????????????CF 3CHF 2?Me????H????Me????Et?????????????i-C 3F 7?Me????H????Me????i-Pr???????????CF 2CHF 2?Me????H????Me????n-Pr???????????CF 2CHF 2?Me????H????Me????CF 3???????????CF 2CHF 2?Me????H????Me????CF 3???????????Me ?Me????H????Me????OMe????????????CH 2CF 3?Me????H????Me????H??????????????CH 2CF 3?Me????H????Me????H??????????????CH 2CF 3?Me????H????Me????H??????????????C 2F 5?Et????H????Me????H??????????????C 2F 5?Me????H????Me????H??????????????C 2F 5?Me????H????Me????H??????????????CF 2CHF 2?Me????H????Me????i-Pr???????????CH 2CF 3?Me????H????Me????H??????????????n-C 3F 7?Me????H????Me????H??????????????i-C 3F 7?Me????H????Me????Ph?????????????CH 2CF 3?Me????H????Me????Ph?????????????CF 2CHF 2?Me????H????Me????Ph?????????????CHF 2Me H Me 2-pyridyl CH 2CF 3Me H Me 2-pyridyl CF 2CHF 2?Me????H????Me????2-ClPh?????????CH 2CF 3?Me????H????Me????2-ClPh?????????CF 2CHF 2?Me????H????Me????2-ClPh?????????CHF 2?Me????H????Me????2-ClPh?????????Et ?Me????H????Me????2-ClPh?????????CBrF 2?Me????H????Me????2-BrPh?????????CH 2CF 3?Me????H????Me????2-MePh?????????CH 2CF 3?Me????H????Me????2-CNPh?????????CH 2CF 3?Me????H????Me????2-FPh??????????CH 2CF 3?Me????H????Me????2,6-F 2Ph??????CH 2CF 3?Me????H????Me????2,4-F 2Ph??????CH 2CF 3?Me????H????Me????2,5-F 2Ph??????CH 2CF 3?Me????H????Me????2-MeOPh????????CH 2CF 3Me H Me 3-Cl-2-pyridyl CH 2CF 3Me H Me 3-Cl-2-pyridyl CF 2CHF 2Me H Me 3-Cl-2-pyridyl CF 3 | R 3?? R 4a? R 4b R 5a?????? R 5b?Me????H????H????Me????????CF 2CHF 2?Me????H????H????Me????????i-C 3F 7?Me????H????H????Me????????CF 2CHF 2?Me????H????H????Me????????CF 2CHF 2?Me????H????H????CF 3??????CF 2CHF 2?Me????H????H????CF 3??????Me ?Me????H????H????OMe???????CH 2CF 3?Me????H????H????H?????????CH 2CF 3?Me????H????H????H?????????CH 2CF 3?Me????H????H????H?????????C 2F 5?Et????H????H????H?????????C 2F 5?Me????H????H????H?????????C 2F 5?Me????H????H????H?????????CF 2CHF 2?Me????H????H????H?????????CH 2CF 3?Me????H????H????H?????????n-C 3F 7?Me????H????H????H?????????i-C 3F 7?Me????H????H????H?????????CH 2CF 3?Me????H????H????H?????????CF 2CHF 2?Me????H????H????H?????????CHF 2?Me????H????H????Ph????????CH 2CF 3?Me????H????H????Ph????????CF 2CHF 2?Me????H????H????Ph????????CH 2CF 3Me H H 2-pyridyl CF 2CHF 2Me H H 2-pyridyl CHF 2?Me????H????H????2-ClPh????Et ?Me????H????H????2-ClPh????CBrF 2?Me????H????H????2-ClPh????CH 2CF 3?Me????H????H????2-ClPh????CH 2CF 3?Me????H????H????2-ClPh????CH 2CF 3?Me????H????H????2-BrPh????CH 2CF 3?Me????H????H????2-MePh????CH 2CF 3?Me????H????H????2-CNPh????CH 2CF 3?Me????H????H????2-FPh?????CH 2CF 3?Me????H????H????2,6-F 2Ph?CH 2CF 3?Me????H????H????2,4-F 2Ph?CH 2CF 3?Me????H????H????2,5-F 2Ph?CF 2CHF 2?Me????H????H????2-MeOPh???CF 3 |
| R 3?? R 4a? R 4b????? R 5a?????? R 5bMe H Me 3-Cl-2-pyridyl CHF 2Me H Me 3-Cl-2-pyridyl CBrF 2Me H Me 3-F-2-pyridyl CH 2CF 3?Me????H????Me????3-CF 3-2-??????CH 2CF 3Pyridyl Me H Me 3-Me-2-CH 2CF 3Pyridyl Me H Me 3-Br-2-pyridyl CF 3Me H Me 3-Br-2-pyridyl CH 2CF 3Me H Me 3-Br-2-pyridyl CF 2CHF 2Me H Me 3-Br-2-pyridyl CClF 2?Me????Me???H?????H??????????????CHF 2?Me????Me???H?????H??????????????CH 2CF 3?Et????Me???H?????H??????????????CH 2CF 3?Me????Me???H?????Me?????????????CH 2CF 3?Me????Me???H?????Et?????????????CH 2CF 3?Me????Me???H?????Me?????????????CF 2CHF 2?Me????Me???H?????Et?????????????CHF 2?Me????Me???H?????Me?????????????CHF 2?Me????Me???H?????Me?????????????CBrF 2?Me????Me???H?????Me?????????????CHF 2?Et????Me???H?????Me?????????????CH 2CF 3?Me????Me???H?????Me?????????????Et ?Me????Me???H?????Me?????????????n-Pr ?Me????Me???H?????Me?????????????CH 2C 2F 5?n-Pr??Me???H?????Me?????????????CH 2CF 3?Me????Me???H?????Me?????????????CF 3?Et????Me???H?????Me?????????????C 2F 5?Me????Me???H?????Et?????????????CHF 2?Me????Me???H?????n-Pr???????????CH 2CF 3?Me????Me???H?????i-Pr???????????CHF 2?Me????Me???H?????Cl?????????????CH 2CF 3?Me????Me???H?????F??????????????CH 2CF 3?Me????Me???H?????Me?????????????CH 2Cl ?Me????Me???H?????Me?????????????CClF 2?Me????Me???H?????Me?????????????CH 2CH 2Cl ?Me????Me???H?????M??????????????n-C 3F 7 | R 3?? R 4a? R 4b?????? R 5a???? R 5bMe H H 3-Cl-2-pyridyl CHF 2Me H H 3-Cl-2-pyridyl CBrF 2Me H H 3-Cl-2-pyridyl CH 2CF 3?Me????H????H????3-CF 3-2-??????CH 2CF 3Pyridyl Me H H 3-Me-2-CF 2CHF 2Pyridyl Me H H 3-Cl-2-pyridyl CH 2CF 3Me H H 3-Cl-2-pyridyl CH 2CF 3Me H H 3-F-2-pyridyl CF 3Me H H 3-Br-2-pyridyl CClF 2Me H H 3-Br-2-pyridyl CH 2CF 3Me H H 3-Br-2-pyridyl CF 3Me H H 3-Br-2-pyridyl CF 3?Me????H????Cl???Et?????????????CHF 2?Me????H????Cl???Me?????????????CH 2CF 3?Me????H????Cl???Et?????????????CH 2CF 3?Me????H????Cl???Me?????????????CH 2CF 3?Me????H????Cl???Me?????????????CH 2CF 3?Me????H????Cl???Me?????????????CF 2CHF 2?Et????H????Cl???Me?????????????CHF 2?Me????H????Cl???Me?????????????CHF 2?Me????H????Cl???Me?????????????CBrF 2?Me????H????Cl???Me?????????????CHF 2?n-Pr??H????Cl???Me?????????????CH 2CF 3?Me????H????Cl???Me?????????????Et ?Et????H????Cl???Me?????????????n-Pr ?Me????H????Cl???Et?????????????CH 2C 2F 5?Me????H????Cl???n-Pr???????????CH 2CF 3?Me????H????Cl???i-Pr???????????CF 3?Me????H????Cl???Cl?????????????C 2F 5?Me????H????Cl???F??????????????CHF 2?Me????H????Cl???Me?????????????CH 2CF 3?Me????H????Cl???Me?????????????CHF 2?Me????H????Cl???Me?????????????CH 2CF 3?Me????H????Cl???Me?????????????CH 2CF 3?Me????H????Cl???Me?????????????CH 2Cl |
| R 3? R 4a? R 4b R 5a???????? R 5b?Me??Me????H????Me??????????i-C 3F 7?Me??Me????H????Me??????????Allyl ?Me??Me????H????Me??????????CF 2CHF 2?Me??Me????H????Me??????????i-C 3F 7?Me??Me????H????Me??????????CF 2CHF 2?Me??Me????H????Me??????????CF 2CHF 2?Me??Me????H????CF 3????????CF 2CHF 2?Me??Me????H????CF 3????????Me ?Me??Me????H????OMe?????????CH 2CF 3?Me??Me????H????H???????????CH 2CF 3?Me??Me????H????H???????????CH 2CF 3?Me??Me????H????H???????????C 2F 5?Et??Me????H????H???????????C 2F 5?Me??Me????H????H???????????C 2F 5?Me??Me????H????H???????????CF 2CHF 2?Me??Me????H????H???????????CH 2CF 3?Me??Me????H????H???????????n-C 3F 7?Me??Me????H????H???????????i-C 3F 7?Me??Me????H????H???????????CH 2CF 3?Me??Me????H????H???????????CF 2CHF 2?Me??Me????H????H???????????CHF 2?Me??Me????H????Ph??????????CH 2CF 3?Me??Me????H????Ph??????????CF 2CHF 2?Me??Me????H????Ph??????????CH 2CF 3Me Me H 2-pyridyl CF 2CHF 2Me Me H 2-pyridyl CHF 2?Me??Me????H????2-ClPh??????Et ?Me??Me????H????2-ClPh??????CBrF 2?Me??Me????H????2-ClPh??????CH 2CF 3?Me??Me????H????2-ClPh??????CH 2CF 3?Me??Me????H????2-ClPh??????CH 2CF 3?Me??Me????H????2-BrPh??????CH 2CF 3?Me??Me????H????2-MePh??????CH 2CF 3?Me??Me????H????2-CNPh??????CH 2CF 3?Me??Me????H????2-FPh???????CH 2CF 3?Me??Me????H????2,6-F 2Ph???CH 2CF 3?Me??Me????H????2,4-F 2Ph???CH 2CF 3 | ? R 3? R 4a? R 4b? R 5a???????? R 5b??Me????H????Cl????Me??????????CClF 2??Me????H????Cl????Me??????????CH 2CH 2Cl ??Me????H????Cl????Me??????????n-C 3F 7??Me????H????Cl????Me??????????i-C 3F 7??Me????H????Cl????Me??????????Allyl ??Me????H????Cl????CF 3????????CF 2CHF 2??Me????H????Cl????CF 3????????i-C 3F 7??Me????H????Cl????OMe?????????CF 2CHF 2??Me????H????Cl????H???????????CF 2CHF 2??Me????H????Cl????H???????????CF 2CHF 2??Me????H????Cl????H???????????Me ??Et????H????Cl????H???????????CH 2CF 3??Me????H????Cl????H???????????CH 2CF 3??Me????H????Cl????H???????????CH 2CF 3??Me????H????Cl????H???????????C 2F 5??Me????H????Cl????H???????????C 2F 5??Me????H????Cl????H???????????C 2F 5??Me????H????Cl????H???????????CF 2CHF 2??Me????H????Cl????H???????????CH 2CF 3??Me????H????Cl????H???????????n-C 3F 7??Me????H????Cl????Ph??????????i-C 3F 7??Me????H????Cl????Ph??????????CH 2CF 3??Me????H????Cl????Ph??????????CF 2CHF 2Me H Cl 2-pyridyl CHF 2Me H Cl 2-pyridyl CH 2CF 3??Me????H????Cl????2-ClPh??????CF 2CHF 2??Me????H????Cl????2-ClPh??????CH 2CF 3??Me????H????Cl????2-ClPh??????CF 2CHF 2??Me????H????Cl????2-ClPh??????CHF 2??Me????H????Cl????2-ClPh??????Et ??Me????H????Cl????2-BrPh??????CBrF 2??Me????H????Cl????2-MePh??????CH 2CF 3??Me????H????Cl????2-CNPh??????CH 2CF 3??Me????H????Cl????2-FPh???????CH 2CF 3??Me????H????Cl????2,6-F 2Ph???CH 2CF 3??Me????H????Cl????2,4-F 2Ph???CH 2CF 3??Me????H????Cl????2,5-F 2Ph???CH 2CF 3 |
| R 3? R 4a? R 4b??? R 5a?????????? R 5bMe???Me????H????2,5-F 2Ph??????CF 2CHF 2Me???Me????H????2-MeOPh????????CF 3Me Me H 3-Cl-2-pyridyl CHF 2Me Me H 3-Cl-2-pyridyl CBrF 2Me Me H 3-Cl-2-pyridyl CH 2CF 3Me Me H 3-Cl-2-pyridyl CH 2CF 3Me Me H 3-Cl-2-pyridyl CH 2CF 3Me???Me????H????3-CF 3-2-??????CH 2CF 3Pyridyl Me Me H 3-Me-2-CF 2CHF 2Pyridyl Me Me H 3-F-2-pyridyl CF 3Me Me H 3-Br-2-pyridyl CClF 2Me Me H 3-Br-2-pyridyl CH 2CF 3Me Me H 3-Br-2-pyridyl CF 3Me Me H 3-Br-2-pyridyl CF 3Me???Cl????H????Me?????????????CHF 2Me???Cl????H????Et?????????????CH 2CF 3Me???Cl????H????Me?????????????CH 2CF 3Me???Cl????H????Et?????????????CH 2CF 3Me???Cl????H????Me?????????????CH 2CF 3Me???Cl????H????Me?????????????CF 2CHF 2Me???Cl????H????Me?????????????CHF 2Et???Cl????H????Me?????????????CHF 2Me???Cl????H????Me?????????????CBrF 2Me???Cl????H????Me?????????????CHF 2Me???Cl????H????Me?????????????CH 2CF 3n-Pr?Cl????H????Me?????????????Et Me???Cl????H????Me?????????????n-Pr Et???Cl????H????Me?????????????CH 2C 2F 5Me???Cl????H????Et?????????????CH 2CF 3Me???Cl????H????n-Pr???????????CF 3Me???Cl????H????i-Pr???????????C 2F 5Me???Cl????H????Cl?????????????CHF 2Me???Cl????H????F??????????????CH 2CF 3Me???Cl????H????Me?????????????CHF 2Me???Cl????H????Me?????????????CH 2CF 3 | R 3? R 4a? R 4b?? R 5a??????????? R 5b?Me????H????Cl????2-MeOPh????????CH 2CF 3Me H Cl 3-Cl-2-pyridyl CH 2CF 3Me H Cl 3-Cl-2-pyridyl CH 2CF 3Me H Cl 3-Cl-2-pyridyl CF 2CHF 2Me H Cl 3-Cl-2-pyridyl CF 3Me H Cl 3-Cl-2-pyridyl CHF 2Me H Cl 3-F-2-pyridyl CBrF 2?Me????H????Cl????3-CF 3-2-??????CH 2CF 3Pyridyl Me H Cl 3-Me-2-CH 2CF 3Pyridyl Me H Cl 3-Br-2-pyridyl CH 2CF 3Me H Cl 3-Br-2-pyridyl CF 3Me H Cl 3-Br-2-pyridyl CH 2CF 3Me H Cl 3-Br-2-pyridyl CF 2CHF 2?Me????Cl???H?????H??????????????CF 2CHF 2?Me????Cl???H?????H??????????????CH 2CF 3?Me????Cl???H?????H??????????????n-C 3F 7?Me????Cl???H?????H??????????????i-C 3F 7?Me????Cl???H?????Ph?????????????CH 2CF 3?Me????Cl???H?????Ph?????????????CF 2CHF 2?Me????Cl???H?????Ph?????????????CHF 2Me Cl H 2-pyridyl CH 2CF 3Me Cl H 2-pyridyl CF 2CHF 2?Me????Cl???H?????2-ClPh?????????CH 2CF 3?Me????Cl???H?????2-ClPh?????????CF 2CHF 2?Me????Cl???H?????2-ClPh?????????CHF 2?Me????Cl???H?????2-ClPh?????????Et ?Me????Cl???H?????2-ClPh?????????CBrF 2?Me????Cl???H?????2-BrPh?????????CH 2CF 3?Me????Cl???H?????2-MePh?????????CH 2CF 3?Me????Cl???H?????2-CNPh?????????CH 2CF 3?Me????Cl???H?????2-FPh??????????CH 2CF 3?Me????Cl???H?????2,6-F 2Ph??????CH 2CF 3?Me????Cl???H?????2,4-F 2Ph??????CH 2CF 3?Me????Cl???H?????2,5-F 2Ph??????CH 2CF 3?Me????Cl???H?????2-MeOPh????????CH 2CF 3 |
| R 3? R 4a R 4b R 5a????? R 5b?Me??Cl??H????Me???????CH 2CF 3?Me??Cl??H????Me???????CH 2Cl ?Me??Cl??H????Me???????CClF 2?Me??Cl??H????Me???????CH 2CH 2Cl ?Me??Cl??H????Me???????n-C 3F 7?Me??Cl??H????Me???????i-C 3F 7?Me??Cl??H????3-Me-2-??CH 2CF 3Pyridyl Me Cl H Me CF 2CHF 2?Me??Cl??H????CF3??????i-C 3F 7?Me??Cl??H????CF3??????CF 2CHF 2?Me??Cl??H????OMe??????CF 2CHF 2?Me??Cl??H????H????????CF 2CHF 2?Me??Cl??H????H????????Me ?Me??Cl??H????H????????CH 2CF 3?Et??Cl??H????H????????CH 2CF 3?Me??Cl??H????H????????CH 2CF 3 | ? R 3 R 4a? R 4b?? R 5a??????????? R 5bMe Cl H 3-Cl-2-pyridyl CH 2CF 3Me Cl H 3-Cl-2-pyridyl CF 2CHF 2Me Cl H 3-Cl-2-pyridyl CF 3Me Cl H 3-Cl-2-pyridyl CHF 2Me Cl H 3-Cl-2-pyridyl CBrF 2Me Cl H 3-F-2-pyridyl CH 2CF 3??Me??Cl????H????3-CF 3-2-??????CH 2CF 3Pyridyl Me Cl H 3-Br-2-pyridyl CF 3Me Cl H 3-Br-2-pyridyl CH 2CF 3Me Cl H 3-Br-2-pyridyl CF 2CHF 2Me Cl H 3-Br-2-pyridine base CClF 2??Me??Cl????H????H??????????????C 2F 5??Me??Cl????H????H??????????????C 2F 5??Me??Cl????H????H??????????????C 2F 5Me Cl H Me allyl group |
Compound of the present invention usually in comprising liquid diluent, solid diluent or tensio-active agent one of at least agriculture suitable carrier as preparaton or composition.The one-tenth component selections of preparaton or composition is consistent with physicals, method of application and the environmental factors (as stablizing of soil type, humidity) of activeconstituents.Useful preparaton comprises liquid such as solution (comprising emulsible concentrated solution), suspension, emulsion (comprising microemulsion and/or suspoemulsions (suspension emulsion)) etc., and they can be gel by multiviscosisty randomly.Useful preparaton also comprises solid, and as pulvis, powder, granule, pill, tablet, film etc., they can be scattered in water (" wettable ") or water soluble.Activeconstituents can be suspended or solid preparation by (little) encapsulated and further formation; Perhaps, the whole preparation of activeconstituents can be by encapsulated (or " brushing ").The release of activeconstituents can be controlled or delay to capsule.The preparation that can spray can pass through in suitable medium, and the spray consumption is that per hectare about is to several hectolitres.Powerful composition mainly is used as the intermediate of further preparation.
Described composition contains the thinner and the tensio-active agent of effective amount of actives and following approximate range usually, and each measures sum is 100 weight %.
Weight %
Active
Composition
Thinner
Tensio-active agent
Can be scattered in water and water-soluble 5-90 0-94 1-15
Granule, tablet and powder agent
Suspension, emulsion, solution 5-50 40-95 0-15
(comprising emulsible concentrated solution)
Pulvis 1-25 70-99 0-5
Granule and pill 0.01-99 5-99.99 0-15
Powerful composition 90-99 0-10 0-2
" Handbook of Insecticide Dust Diluents andCarriers " (sterilant powder absorption agent and carrier handbook) second edition (Dorland Books at Watkins etc., Caldwell, New Jersey) in the typical solid thinner is described.In Marsden " Solvents Guide " (solvent guide) second edition (Interscience, New York, 1950), typical liquid diluent is described." McCutcheon ' s Detergentsand Emulsifiers Annual " (McCutcheon washing composition and emulsifying agent annual report, AlluredPubl.Corp., Ridgewood, New Jersey) and " Encyclopedia of Surface Active Agents " (tensio-active agent encyclopedia of Sisely and Wood, Chemical Publ.Co., Inc., NewYork, 1964) in enumerated the application of tensio-active agent and recommendation.All preparations can contain additive in a small amount, slowing down foam, caking, burn into microorganism growth etc., or contain thickening material, to increase viscosity.
Tensio-active agent for example comprises: polyethoxylated alcohols, polyethoxylated alkylphenol, polyethoxylated sorbitan fatty acid esters; dialkyl sulfosuccinate; alkyl sulfuric ester, benzene sulfonamide acid esters, organo-siloxane; N; N-dialkyl group taurine ester, lignin sulfonate, naphthalenesulfonate formaldehyde condensation compound; polycarboxylate, and polyoxyethylene/polyoxypropylene block copolymers.Solid diluent for example comprises: clay (as wilkinite, polynite, attapulgite and kaolin), starch, sugar, silicon-dioxide, talcum, diatomite, urea, lime carbonate, yellow soda ash and sodium bicarbonate, and sodium sulfate.Liquid diluent for example comprises: water, N, dinethylformamide, methyl-sulphoxide, N-alkyl pyrrolidone, ethylene glycol, polypropylene glycol, paraffin, alkylbenzene, alkylnaphthalene, sweet oil, Viscotrol C, Toenol 1140, tung oil, sesame oil, Semen Maydis oil, peanut oil, Oleum Gossypii semen, soya-bean oil, rapeseed oil, Oleum Cocois, fatty acid ester, ketone (as pimelinketone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2 pentanone), and alcohols (as methyl alcohol, hexalin, decyl alcohol and tetrahydrofurfuryl alcohol).
Solution (comprising emulsible concentrated solution) can prepare by simply composition being mixed.Pulvis and powder agent can be by mixing and preparing as the grinding of carrying out in hammer mill or fluid energy rolling machine usually.Suspension is usually by the wet-milling preparation, referring to for example U.S.3,060,084.Granule and pill can prepare by active substance being sprayed on the prefabricated granular carrier or passing through agglomeration technique.Referring to: " Agglomeration " of Browning, Chemical Engineering, on December 4th, 1967,147-48 page or leaf; " Perry ' s Chemical Engineer ' sHandbook " the 4th edition (McGraw-Hill, New York, 1963) 8-57 page or leaf and below; With PCT publication WO91/13546.Pill can be as U.S.4, and 172,714 is described and prepare.Can be scattered in water and water-soluble granule can be according to U.S.4, and 144,050, U.S.3,920,442 and DE3,246,493 preparations.Tablet can be according to U.S.5, and 180,587, U.S.5,232,701 and U.S.5,208,030 preparations.Film can be according to GB2, and 095,558 and U.S.3,299,566 preparations.
The further information of relevant formulation art, " The Formulator ' sToolbox-Product Forms for Modern Agriculture (product form of preparation work person work box-modern agriculture) " referring to T.S.Woods, close at " Pesticide Chemistry andBioscience, The Food-Environment Challenge " (sterilant chemistry and bio-science, food-environment challenge), T.Brooks and T.R.Roberts edit, the 9th international sterilant chemistry conference scientific research report collection, Cambridge, 1999, the 120-133 page or leaf.Referring to U.S.3,235,361 the 6th hurdles the 16th walk to the 7th hurdle the 19th row and embodiment 10-41 in addition; U.S.3,309,192 the 5th hurdles the 43rd walk to the 7th hurdle the 62nd row and embodiment 8,12,15,39,41,52,53,58,132,138-140,162-164,166,167 and 169-182; U.S.2,891,855 the 3rd hurdles the 66th walk to the 5th hurdle the 17th row and embodiment 1-4; Klingman work " Weed Control as a Science " (weeds control science), John Wileyand Sons company publishes, New York,, 81-96 page or leaf in 1961; With work such as Hance " WeedControl Handbook " (weeds control handbook) the 8th edition, Blackwell ScientificPublications publishes, Oxford, 1989 years.
In following examples, all per-cents all are weight percentage, and all preparations in a usual manner of all preparations.Compound number is referring to the compound among the concordance list A.
Embodiment A Wettable powder agentCompound 1 65.0% 4-dodecylphenol polyglycol ether 2.0% sodium lignosulfonate 4.0% sodium silicoaluminate 6.0% polynite (through calcining) 23.0%
Embodiment B GranuleCompound 7 10.0% attapulgite particle (low volatility materials, 0.71/0.30mm; The U.S.S.No.25-50 sieve) 90.0%
Embodiment C The pill of extrusion moldingPlain calcium sulphonate 5.0% sodium alkyl naphthalene sulfonate of compound 1 25.0% anhydrous sodium sulphate 10.0% rugose wood 1.0% calcium/magnesium wilkinite 59.0%
Embodiment D Emulsible concentrated solutionAdulterant 10.0% isophorone 70.0% of compound 7 20.0% oil-soluble sulfonic acid salt and Soxylat A 25-7
Embodiment E GranuleCompound 1 0.5% Mierocrystalline cellulose 2.5% lactose 4.0% Semen Maydis powder 93.0%
The compounds of this invention is characterised in that favourable metabolism and/or soil fundamental mode formula, and shows the agricultural of certain limit and the control activity of non-agricultural invertebrate pests.(in specification sheets scope of the present invention, " invertebrate pest control " means the growth (comprising deadly) that suppresses invertebrate pests, significantly reduces other injury that its food ration or insect cause; Relevant express definitions is similar).With regard to this specification sheets, term " invertebrate pests " comprises segmental appendage class, snails, the nematode pests with Economic Importance.Term " segmental appendage class " comprises insect, mite, spider, scorpion, centipede, Scolopendra, ball tide worm and summation guiding principle (symphylans).Term " snails " comprises snail, slug (slugs) and other Stylommatophora (Stylommatophora).Term " threadworms " comprises all worms, as: roundworm, heartworm, phytophagy threadworms (nematoda), fluke (Tematoda), Acanthocephala, and tapeworm (merozoic cestode guiding principle).Those skilled in the art will appreciate that not to be that all compounds have identical effectiveness for all insects.Compound exhibits of the present invention to having the activity of insect of aspects such as agricultural, forestry, greenhouse, nursery, ornamental plant, food and fiber, publilc health and animal health, family expenses and commercial building, houseware and stores of importance economically.These comprise lepidopterous larva, grain silkworm moth larva (armyworms) as Noctuidae family, cutworm (cutworms), looper (loopers), and heliothines (for example: autumn grain silkworm moth larva (Spodoptera fugiperda J.E.Smith), beet grain silkworm moth larva (Spodoptera exigua.H ü bner), black cutworm (Agrotis ipsilon Hufnagel), Caulis et Folium Brassicae capitatae looper (amyloid plaque noctuid, Trichoplusiani H ü bner), tobacco aphid (Heliothis virescens Fabricius)); The moth of Pyralidae family, casebearer, web spinner, taper worm (coneworms), leaf roll cabbageworm and ossified worm (skeletonizers) are (for example: European corn boring worm (Ostrinia nubilalisH ü bner), navel orange worm (Amyelois transitella Walker), Zea mays root web spinner (Crambus caliginosellus Clemens), meadow web spinner (Herpetogrammalicarsislis Walker)); The leaf of Tortricidae family rolls worm (leafrollers), aphid, seed worm (seed worms), and fruitworm (fruit worms) (for example: carpocapsa pononella (Cydia pomonella Linnaeus), the moth-eaten moth (Endopiza viteanaClemens) of glucose berry, east fruit moth-eaten moth (Grapholita molesta Busck)); And many other important economically lepidopterans (for example diamond back moth (Plutella xylostellaLinnaeus), pink bollworm (Pectinophora gossypiella Saunders), gypsymoth (Lymantria dispar Linnaeus)); Blattodea purpose naiad and adult, cockroach (the east cockroach (Blatta orientalisLinnaeus) for example that comprises Blattollidae and Blattidae family, Asia cockroach (Blatella asahinai Mizukubo), Germany cockroach (Blattella germanica Linnaeus), brown band cockroach (Supella longipalpaFabricius), american cockroach (Periplaneta americana Linnaeus), brown cockroach (Periplaneta brunnea Burmeister), Ma Dela island cockroach (Leucophaeamaderae Fabricius)); Coleoptera take the photograph leaf larva and adult, weevil (the boll weevil (Anthonomus grandisBoheman) for example that comprises Anthribidae, Bruchidae and Curculionidae family, rice water weevil (rice water weevil, Lissorhoptrus oryzophilusKuschel), paddy weevil (Sitophilus granarius Linnaeus), rice weevil (Sitophilus oryzae Linnaeus)); The flea beetle of Chrysomelidae family, cucumber beetle, rootworm, chrysomelid, colorado potato bug and beet gelechiid (for example Colorado colorado potato bug (Leptinotarsa decemlineata Say), west corn rootworm (Diabroticavirgifera virgifera LeConte)); The chafer of Scarabaeidae family and other beetle (for example Japanese beetle (Popillia japonica Newman) and European chafer (Rhizotrogus majalis Razoumowsky)); The Carpet of Dermestidae family; Elaterid iron wire worm (wireworms); The ambrosia beetle of Scolytidae family (barkbeetles)) and the meal beetle worm of Tenebrionidae.Comprise in addition: the adult of Dermaptera and larva comprise the DIWUGONG (for example European DIWUGONG (Forficula auriculariaLinnaeus), unregistered land centipede (Chelisoches morio Fabricius)) of autumn Sou section; Adult of Hemiptera and Homoptera and naiad, fleahopper as Miridae family, the cicada of Cicadidae family, the leafhopper of Cicadellidae family (for example Empoasca spp.), the planthopper of tree of heaven chicken family of section and Delphacidae family, the horned frog of Membracidae family, the wood louse of Psyllidae family, the aleyrodid of Aleyrodidae family, the aphid of Aphidiadae family, the Phylloxera of Phylloxera Aphididae family, the mealybug of Pseudococcidae family, wax coccidae family, the scale insect (scales) of family of Hesuo a red-spotted lizard section of Diaspididae family, the lace bug of Tingidae family, the stinkbug of Pentatomiddae family, the China bug of Lygaeidae family (for example Blissus spp.) and other seed bugs, the froghopper of Cercopidae family, the squash bug of Coreidae family, and trombiculid of Pyrrhocoridae family (red bugs) and cotton stinkbug.The adult and the naiad that also comprise Acarina, red spider and congo red tetranychid (for example European congo red tetranychid (Panonychus ulmi Koch) as Tetranychidae family, 2 red spider (two spottedspider mite, Tetranychus urticae Koch), McDaniel mite (Tetranychusmcdaniele McGregor)), the flatmite (for example oranges and tangerines flatmite (Brevipalpus lewisi McGregor)) of family of the sufficient spider of hair section, the rust mite of Eriophyidae family and bud mite (budmites), and other takes the photograph tetranychid and to the healthy important mite of humans and animals, it is the dirt mite (dust mites) of Epidermoptidae family, the follicle mite of Demodicidae family, eat the paddy mite of family of sweet mite section, the flat lice of hard tick section class (deer lice (deer tick for example, Ixodesscapularis Say), Australia paralysis lice (Australian paralysis tick, Ixodesholocyclus Neumann), America dog lice (Dermacentor variabilis Say), lonely star lice (lone star tick, and family of scabies mite lice section Amblyomma americanum Linnaeus)),, the horse scabies mite and the itch mite of Pyemotidae family and Sarcoptidae family; The adult of Orthoptera and adult not, comprise that grasshopper, locust and cricket (for example migrate grasshopper (Melanoplussanguinipes Fabricius for example, M.Differentialis Thomas), America grasshopper (for example Schistocerca americana Drury), Desert locusts (Schistocerca gregariaForskal), migrate locust (Locusta migratoria Linnaeus), acheta domestica (Achetadomesticus Linnaeus), mole cricket (Gryllotalpa Spp.)); The adult of Diptera class and adult not, comprise: the beet gelechiid, midge, fruit bat (Tephritidae), frit fly (for example Oscinella frit Linnaeus), the soil maggot, housefly (for example Musca domesticaLinnaeus), little housefly (Fannia canicularis Linnaeus for example, F.femoalisStein), tatukira (for example Stomoxys calcitrans Linnaeus), face fly (faceflies), horn fly, calliphorid (blow flies, Chrysomya spp. for example, Phormia spp.) and other fly shape fly insect (muscoid fly pests), horse botfly (for example Tabanus spp.), skin fly (for example Gastrophilus spp., Oestrus spp.), gadfly (for example Hypodermaspp.), deerfly (for example Chrysops spp.), keds (for example Melophagus ovinusLinnaeus), and other Brachycera, mosquito (Aedes spp. for example, Anopheles spp., Culex spp.), black fly (for example Prosimulium spp., Simulium spp.), midge, sand fly, sciarids and other Nemocera; The adult of Thysanoptera class and adult not comprise that onion thrips (Thrips tabaci Lindeman) and other take the photograph the leaf thrips; The hexapeopoda pest of Hymenoptera class, comprise: ant (for example red worker carpented ant (Camponotus ferrugineus Fabricius), black-labour carpented ant (Camponotus pennsylvanicus DeGeer), little red ant (Monomoriumpharaonis Linnaeus), little fiery ant (Wasmannia auropunctata Roger), fire ant (Solenopsis geminata Fabricius), the infrared ant of flaring up (Solenopsisinvicta Latreille), Argentine ant (Iridomyrmex humilis Mayr), brown mad ant (Paratrechina longicornis Latreille), Pavement Ant (Tetramoriumcaespitum Linnaeus), meadow, America ant (Lasius alienus F_ster), smelly family ant (Tapinoma sessile Say)), honeybee (comprising carpenter bee), wasp, the brown yellow peak of aureus wasp; The insect pest of Isoptera, comprise: eastern U.S. reticulitermes flavipe (Reticulitermesflavipes Kollar), west U.S. reticulitermes flavipe (Reticulitermes hesperus Banks), Taiwan formosanes (Coptotermes formosanus Shiraki) is moved the principal columns of a hall termite that dwells (Incisitermes immigrans Snyder) and other and is had the termite of importance economically; The insect pest of Thysanura is as silverfish (Lepisma saccharina Linnaeus) and tame silverfish (Thermobia domestica Packard); The insect pest of Mallophaga, and comprise head louse (Pediculus humanus capitis De Geer), body louse (Pediculus humanushumanus Linnaeus), chick poultry louse (Menacanthus stramineus Nitszch), dog stings lice (dog biting louse, Trichodectes canis De Geer), fine hair lice (fluff louse, Goniocotes gallinae De Geer), sheep body louse (sheep bodylouse, Bovicola ovis Schrank), wealthy chest blood lice (short-nosed cattlelouse, Haematopinus eurysternus Nitzsch), Linognathus vituli (long-nosedcattle louse, Linognathus vituli Linnaeus) and other are attacked the sucking parasitic lice (sucking parasitic lice) of humans and animals and are chewed parasitic lice (chewingparasitic lice); The insect pest of Siphonaptera, comprise Xenopsyllacheopis (oriental rat flea, Xenopsylla cheopis Rothschild), cat flea (Ctenocephalides felisBouche), dog flea (Ctenocephalides canis Curtis), hen flea (Ceratophyllus gallinae Schrank), echidnophaga gallinacea (sticktight flea, Echidnophaga gallinacea Westwood), the louse of Pulex irritans (Pulex irritansLinnaeus) and other torment Mammals and birds.Other segmental appendage insect of containing comprises: the spider of Araneida, as brown living in seclusion spider (brown recluse spider, Loxoscelesreclusa Gertsch ﹠amp; Mulaik) and black widow spider (Latrodectus mactansFabricius), and Scutigeromorpha purpose centipede, as tame centipede (Scutigeracoleoptrata Linnaeus).Activity also comprises nematoda, the merozoic cestode guiding principle, the member of Trematoda and Acanthocephala, comprise important economically Strongylida order, the Ascaridida order, pinworm order (Oxyurida), the Rhabditida order, Spirurida order and Enoplida purpose member, the Agricultural pests important economically (the Ma Shi golden nematode that belongs to of Meloidogyne for example as (but being not limited to), the eelworm that Pratylenchus belongs to, the jute root nodule nematode that Trichodorus belongs to etc.) and animal and human's healthy insect (for example, the fluke that all are important economically, tapeworm, and roundworm, Stongylus vulgaris as horse, the Toxocara canis of dog, the Haemonchuscontortus of sheep, the Dirofilaria immitis Leidy of dog, the Anoplocephalaperfoliata of horse, the Fasciola hepatica Linnaeus of ruminating animal, etc.).
Compound of the present invention has extra high activity to following each purpose insect: lepidopteran (Alabama argillacea H ü bner (cotton leaf ripple noctuid) for example, Archips argyrospilaWalker (the yellow volume of fruit moth), A.rosana Linnaeus (European leaf roller) and other Archips kind, Chilo suppressalis Walker (striped rice borer), Cnaphalocrosis medinalis Guenee (rice leafroller), Crambuscaliginosellus Clemens (Zea mays root net snout moth's larva), Crambus teterrellus Zincken (annual bluegrass crambid), Cydia pomonella Fabricius (the moth-eaten moth of apple), Earias insulanaBoisduval (the real moth of cotton spot), Earias vittella Fabricius (spottedbollworm), Helicoverpa virescens H ü bner (Ammerican bollworm), Helicoverpa zea Boddie (corn earworm), Heliothis virescens Fabricius (Heliothis virescens), Herpetogramma licarsisalis Walker (sod webworm), Lobesis botrana Denis ﹠amp; Schifferm ü ller (glucose steinernema), Pectinophoragossypiella Saunders (pink bollworm), Phyllocnistis citrellaStainton (tangerine leaf mining first), Pieris brassicae Linnaeus (large white butterfly), Pieris papae Linnaeus (pieris rapae), Plutella xylostella Linnaeus (small cabbage moth), Spodoptera exigua H ü bner (beet armyworm), Spodoptera lituraFabricius (prodenia litura, cluster caterpillar), Spodoptera frugiperdaJ.E.Smith (meadow mythimna separata), Trichoplusia ni H ü bner (cabbage looper) and Tutaabsoluta Meyrick (tomato leafminer)).Compound of the present invention also has commercial tangible activity to the member of Homoptera, comprise: Acyrthisiphon pisum Harris (pea aphid), Aphis craccivora Koch (cowpea aphid), Aphis fabae Scopoli (black bean aphid), Aphis gossypii Glover (cotten aphid, the melon aphid), Aphis pomi De Geer (apple aphid), Aphis spiraecola Patch (spiraea aphid), Aulacorthum solaniKaltenbach (foxglove does not have the net aphid), Chaetosiphon fragaefolii Cockerell (knurl nail hair aphid in the strawberry), Diuraphis noxia Kurdjumov/Mordvilko (Russian grain aphid), Dysaphis plantaginea Paaserini (rounded tail aphid before the car), Eriosoma lanigerum Hausmann (woolly apple aphid), Hyalopterus pruni Geoffroy (mealy plum aphid), Lipaphis erysimi Kaltenbach (aphid), Metopolophiumdirrhodum Walker (paddy aphid), Macrosipum euphorbiae Thomas (potato aphid), Myzus persicae Sulzer (peach-potato aphid, black peach aphid), Nasonovia ribisnigri Mosley (lettuce is patched up Macrosiphus spp), Pemphigus spp. (root aphid and glucose root wart aphid), Phopalosiphum maidis Fitch (corn leaf aphids), Rhopalosiphum padi Linnaeus (bird cherry-oat aphid), Schizaphisgraminum Rondani (green bugs), Sitobion avenae Fabricius (grain aphid), Therioaphis maculata Buckton (clover spot aphid), Toxoptera aurantiiBoyer de Fonscolombe (tangerine sound aphid) and Toxoptera citricida Kirkaldy (tropical black citrus aphid); Adelges spp. (adelgid); Phylloxera devastatrixPergande (U.S. walnut Phylloxera); Bemisia tabaci Gennadius (tobacco aleyrodid, sweet potato whitefly); Bemisia argentifolii Bellows ﹠amp; Perring (silverleafwhitefly), Dialeurodes citri Ashmead (citrus whitefly) and Trialeurodesvaporariorum Westwood (greenhouse whitefly); Empoasca fabae Harris (broad bean Empoasca spp), Laodelphax striatellus Fallen (little brown back rice plant hopper), Macrolestesquadrilineatus Forbes (Macrosteles sexnotata), Nephotettix cinticeps Uhler (tea Empoasca spp), Nephotettix nigropictus St
L (rice green leafhopper), Nilaparvatalugens St
L (Nilaparvata lugen (brown planthopper)), Peregrinus maidis Ashmead (corn plant hopper), Sogatella furcifera Horvath (carrying on the back the rice lice in vain), Sogatodes orizicola Muir (rice delphacid), Typhlocyba pomaria McAtee (the white jassids of apple), Erythroneoura spp. (glucose Erythroneura spp); Magicidada septendecim Linnaeus (phase cicada); Icerya purchasi Maskell (icerya purchasi), Quadraspidiotusperniciosus Comstock (San Jose scale); Planococcus citri Risso (citrus mealy bug); Pesudococcus spp. (other mealybug complex body): Cacopsylla pyricolaFoerster (pear psyllid), Trioza diospyri Ashmead (kaki lice).These compounds also double wing purpose member have activity, comprise: Acrosternum hilare Say (Nezara viridula smaragdula Fabricius.), Anasa tristis De Geer (the green stinkbug of pumpkin), Blissus leucopterusleucopterus Say (China bug), Corythuca gossypii Fabricius (web stinkbug (cotton lace bug)), Cyrtopeltis modesta Distant (tomato bug), Dysdercus suturellus Herrich-Sch_ffer (the cotton black red stinkbug of wing), Euchistusservus Say (brown smelly stinkbug), Euchistus variolarius Palisot de Beauvois (a bit brown stinkbug), Graptosthetus spp. (aphid complex body), Leptoglossuscorculus Say (pine nut beak coried), Lygus lineolaris Palisot de Beauvois (tarnished plant bug), Nezara viridula Linnaeus (Nezara viridula smaragdula Fabricius.), Oebalus pugnaxFabricius (niphe elongata), Oncopeltus fasciatus Dallas (large milkweed bug), Pseudatomoscelis seriatus Reuter (cotton fleahopper).Other insect order of being prevented and treated by The compounds of this invention comprises: Thysanoptera (Frankliniella occidentalisPergande (alfalfa thrips) for example, Scirthothrips citri Moulton (the real thrips of tangerine), Sericothrips variabilis Beach (soybean thrips), with Thrips tabaciLindeman (onion thrips)), and Coleoptera (Leptinotarsa decemlineata Say (colorado potato bug) for example, Epilachna varivestis Mulsant (mexican bean ladybird), and Agriotes, the iron wire worm of Athous and Limonius kind).
Compound of the present invention also can with one or more other bioactive compounds or reagent mix, to form multicomponent sterilant, produce wider agricultural scope, described other bioactive compounds or reagent comprise: sterilant, mycocide, nematocides, sterilant, miticide, growth regulator (as taking root stimulant (rooting stimulants)), chemosterilant, chemical information thing (semiochemicals), wormer, attractant, pheromone, the stimulant of ingesting (feeding stimulants), other bioactive compounds or entomiasis indigenous bacteria, virus or fungi.Therefore, composition of the present invention can further comprise at least a additional bioactive compounds or the reagent of biologic effective dose.Compound of the present invention can be prepared with following each routine bioactive compounds or reagent: sterilant, and as avermectin (abamectin), Ortho 12420, the pyrrole worm is clear, avermectin (avermectin), Ai Zhading, R-1582, bifenthrin, Bifenazate, Buprofezin, carbofuran, fluorine azoles worm is clear, UC 62644, Chlorpyrifos 94, chlorpyrifos_methyl, chromafenozide, clothianidin, cyhalothrin, β-cyhalothrin, (RS) cyhalothrin, λ-cyhalothrin, Cypermethrin, fly eradication amine, Deltamethrin, it is grand to kill mite sulphur, diazinon, TH-6040, the luxuriant ether of Rogor Evil, emamectin, 5a,6,9,9a-hexahydro-6,9-methano-2,4, esfenvalerate, ethiprole, fenothiocarb, ABG-6215, Fenvalerate, azoles mite ester is killed the chrysanthemum ester, sharp strength spy, flonicamid, flucythrinate, taufluvalinate, flufenoxuron, Dyfonate, RH 0345, fluorine bell urea, Provado oxadiazole worm, propylamine phosphorus, the fluorine third oxygen urea, Phosphothion, Halizan, acephatemet, methidathion, methomyl, Entocon ZR 515, methoxychlor, monocrotophos, Runner, WL 35651, Rimon, thioxamyl, one six zero five, methyl 1, permethrin, phorate, zolone, R-1504, phosphamidon, Aphox, Profenofos, pymetrozine, pyridalyl, pyriproxyfen, tubatoxin, SPINOSAD 105, second Toyodan, RH-5992, Teflubenzuron, tefluthrin, Terbufos, tetrachlorvinphos, thiacloprid, thiamethoxam, UC-51762, disosultap, tralomethrin, Trichlorphon and desinsection are grand; Mycocide, as the thiadiazoles element, the phonetic chrysanthemum ester of nitrile, F-1991, miewensu, Bordeaux mixture (Basic Chrome Sulphate), bromuconazole, carpropamide, captafol, Vancide 89, derosal, chloroneb, m-tetrachlorophthalodinitrile, Cupravit, mantoquita, cyflufenamid, cymoxanil, cyproconazole encircles third pyrimidine, (S)-3,5-two chloro-N-(3-chloro-1-ethyl-1-methyl-2-oxygen propyl group)-4-methyl benzamide (RH 7281), diclocymet (S-2900), diclomezine, dicloran; the luxuriant azoles of Evil, (S)-3,5-dihydro-5-methyl-2-methyl sulfo--5-phenyl-3-phenylamino-4H-imidazol-4-one (RP407213), dimethomorph, dimoxystrobin, alkene azoles alcohol, alkene azoles alcohol-M, dodine, Hinosan, oxole bacterium ， oxazole copper bacterium, fenamidone, fenarimol, RH-7592, fencaramide (SZX0722), fenpiclonil, fenpropidin, fenpropimorph, fentinacetate, fentin hydroxide, fluazinam, fluorine biphenyl bacterium (RPA 403397), Fluquinconazole, fluzilazol, fultolanil, flutriafol, Phaltan, fosetyl, Furalaxyl, furan pyrazoles spirit (S-82658), own azoles alcohol, cycltebuconazole, different third is fixed, Fujione, kasugamycin, imines bacterium, zinc manganese ethylenebisdithiocarbamate, maneb, mefenoxam, third oxygen embroidery amine that goes out, metaxanin encircles penta azoles bacterium, fork phenalgin acid amides (SSF-126), nitrile bacterium azoles, the spirit of Neo-Asozin (ferric methylarsonate) Evil frost, Topaze, pencycuron, Prochloraz, hundred dimension spirits encircle third azoles, pyrifenox, pyraclostrobin, pyrimethanil, pyroquilon, the luxuriant amine of quinoxyfen ， Luo Evil, SULPHUR POWDER, tebuconazole, fluorine ether azoles, Apl-Luster, thifluzamide, thiophanate methyl, thiram, tiadinil, triazolone, Triabimeno I, tricyclazole, trifloxystrobin, triticonazole, validamycin, and vinclozolin; Nematocides, as aldicarb, thioxamyl, and Nemacur; Sterilant is as Streptomycin sulphate; Miticide, as U-36059, chinomethionate, G-23922, cyhexatin, Mitigan, Hooker HRS 16, Te Ben oxazole, fenazaquin, fenbutatin oxide, Fenvalerate, azoles mite ester, hexythiazox, propargite, pyridaben, and tebufenpyrad; And biological reagent, as bacillus thuringiensis (Bacillus thuringiensis), comprise damp subspecies (aizawai) and Ku Er Stark subspecies (kurstaki), bacillus thuringiensis delta-endotoxin (delta endotoxin), baculovirus, and carnivorism bacterium, virus and fungi.
The generalized reference document of relevant these agricultural protective agents is: " The Pesticide Manual " (sterilant handbook), and the 12 edition, C.D.S.Tomlin publishes; British Crop ProtectionCouncil (the Britain crop protection council), Farnham, Surrey; U.K., 2000.
Be used for comprising with the preferred sterilant and the tick-killing agent of compound of the present invention: pyrethroids, as Cypermethrin, (RS) cyhalothrin, cyfloxylate, β-cyfloxylate, esfenvalerate is killed chrysanthemum ester and tralomethrin; Amino formate, as fenothicarb, methomyl, thioxamyl, and UC-51762; Neonicotinoids, as clothianidin, Provado, and thiacloprid; Neuronal sodium channel plugging agent (neuronal sodium channelblockers) ， such as oxadiazole worm; The desinsection Macrolide, as SPINOSAD 105, avermectin (abamectin), avermectin (avermectin), and emamectin; γ-An Jidingsuan (GABA) antagonist (antagonists), as 5a,6,9,9a-hexahydro-6,9-methano-2,4, ethiprole and sharp strength spy; Sterilant urea, grand as flufenoxuron and desinsection; Luxuriant ether of neotonin ， such as Evil and pyriproxyfen; Pymetrozine; And U-36059.Be used for comprising bacillus thuringiensis and bacillus thuringiensis delta-endotoxin with the preferred biological reagent of compound of the present invention, and naturally occurring and viral pesticide genetic improvement, comprise the member and the entomophagous fungi of baculovirus order (baculoviridae).
Most preferred mixture comprises: the compound of the present invention and (RS) mixture of cyhalothrin; The mixture of compound of the present invention and cyfloxylate; The mixture of compound of the present invention and β-cyfloxylate; The mixture of compound of the present invention and esfenvalerate; The mixture of compound of the present invention and methomyl; The mixture of compound of the present invention and Provado; The mixture of compound of the present invention and thiacloprid; Compound of the present invention is Yu the mixture of oxadiazole worm; The mixture of compound of the present invention and avermectin (abamectin); The mixture of compound of the present invention and 5a,6,9,9a-hexahydro-6,9-methano-2,4; The mixture of compound of the present invention and ethiprole; Compound of the present invention and sharp strength spy's mixture; The mixture of compound of the present invention and flufenoxuron; The mixture of compound of the present invention and pyriproxyfen; The mixture of compound of the present invention and pymetrozine; The mixture of compound of the present invention and U-36059; The mixture of compound of the present invention and bacillus thuringiensis; And the mixture of compound of the present invention and bacillus thuringiensis delta-endotoxin.
In some cases, with have similar prevention and treatment range but the combination of other invertebrate pest control compounds of the different modes of action or reagent is particularly advantageous for drag control (resistance management).Therefore, composition of the present invention can further comprise at least a additional of biologic effective dose and has similar prevention and treatment range but the invertebrate pest control compound or the reagent of the different modes of action.Genetic improvement is contacted with the The compounds of this invention of biologic effective dose with the plant of expression plant protection compound (for example protein) or the place of this plant, wider plant protection scope also can be provided, and control is particularly advantageous for drag.
By to the environment of insect (comprising agricultural and/or non-agricultural place that insect occurs), to the zone of need protection or directly use one or more compounds of the present invention with biologic effective dose to the insect of needs control; invertebrate pests can be prevented and treated, and realizes the protection to farm crop, garden crop and special crop and animal and human's class health.Therefore; the present invention comprises that further a kind of Ye Ju of control and soil occupy the method for invertebrate pests and protection agricultural and/or non-agricultural crop; comprise invertebrate pests or its environment are contacted with one or more compounds of the present invention of biologic effective dose, or contact with at least a additional bioactive compounds or combination of agents thing with containing at least a described compound compositions or contain at least a described compound.Preferred contact method is by spraying.The granular composition that perhaps, can contain The compounds of this invention to leaf or soil application.By contacting the plant absorbing that causes with the composition that contains The compounds of this invention by plant, compound of the present invention is able to effective release, and described composition soaks into, is used for granular preparation, the incubator processing of soil as the soil of liquid adjustments or transplants dipping and use.Other contact method comprise by the spraying of direct or anelasticity, aviation spray, plant that skin, microcapsule, system absorb, bait lures, ear tag (eartags), bolus, atomizer, fumigant, aerosol, dust and many other methods use compound of the present invention or composition.
Composition of the present invention can be mixed the edible bait of invertebrate pests, or mix in device such as the trap etc.Particle or bait contain the activeconstituents of 0.01-5%, the moisture content that contains reagent (one or more) of 0.05-10% and the plant powder of 40-99%; can prevent and treat soil pests effectively with very low rate of application, particularly and for the fatal activeconstituents dosage for by ingesting but not direct contact.
Compound of the present invention can be used with its its pure state, but what more often use is a kind of preparaton, and it contains suitable carriers, thinner and tensio-active agent, and may combine with food according to the whole purposes of being considered.Preferred application process relates to the water dispersion or the treated oil solution of described compound.Combine the effectiveness that strengthens compound usually with spray oil, spray oil enriched material, spreader-sticker, auxiliary material, other solvent and synergistic agent such as Piperonyl Butoxide.
The rate of application (i.e. " biologic effective dose ") that effective dispensary needs will depend on such as following factors: need the kind of the invertebrate pests of control, the life cycle of insect, life stage, the size of insect, season, host crop or animal, feeding habit, ambient humidity, stable, etc.In the ordinary course of things, the rate of application of the about 0.01-2kg activeconstituents of per hectare is enough to prevent and treat the insect in the agroecosystem, but few to 0.0001 kg/ha can be enough, and also can need nearly 8 kg/ha.For non-agricultural, the effective level scope is about 1.0-50mg/m
2, but few to 0.1mg/m
2Can be enough, and also can need nearly 150mg/m
2Those skilled in the art can easily determine the necessary biologic effective dose of invertebrate pest control of desired degree.
Test in the following biological Examples of the present invention has illustrated the preventing efficiency of The compounds of this invention for specific insect." preventing efficiency " expression stops the arthropodan growth that causes that a large amount of reductions are supplied with.Yet the pest control provide protection that described compound provides is not limited to these kinds.For the description of compound, referring to concordance list A-E.Used following abbreviation: t to be uncle in following concordance list, n is for just, and i is different, and s is secondary, and Me is a methyl, and Et is an ethyl, and Pr is a propyl group, and Br is a butyl; Correspondingly, i-Pr is a sec.-propyl, and s-Bu is a sec-butyl, or the like, Ac is COCH
3Abbreviation " Ex. " representative " embodiment ", numeral thereafter shows that described compound prepares in that embodiment.
Concordance list A 
Compound R
2R
3R
4M R
5Fusing point ℃ (Ex.1) Me H H 2 2-Me-4-F 249 2 i-Pr H H 2 2-Me-4-Cl＞250 3 n-Pr H H 2 2-Me-4-Cl 212 4 i-Bu H H 2 2-Me-4-Cl * * * 5 Me Me H 2 2-Me-4-Cl * * * 6 Et H H 2 2-Me-4-Cl * * * 7 Me H H 2 2-Me-4-Cl 244 8 allyl H H 22,4-di-Me 243 9 ring-Pr H H 2 2-Me-4-Cl 246 10 H H H 2 2-Me-4-Cl * * * 11 Me H H 2 2-Me-4-OCF3＞250 12 Me H H 1 4-OCF
3＞250 13 Me H H 22,4-di-Cl＞250 14 Me H H 2 2-Me-5-Cl 241 15 Me H H 2 2-Me-3-Cl＞250 16 Me H H 1 2-Me 236 17 Me H H 2 2-Me-4-Br 234 18 Me H H 1 4-i-Pr＞250 19 Me H H 1 4-NHAc 224 20 Me H H 1 2-Br 210 21 Me H H 1 2-OPh 193 22 Me H H 1 4-OMe 188 23 Me H H 1 4-(morpholine-4-yl) 246 24 Me H H 1 2-F 177 25 Me H H 1 4-I 235 26 Me H H 2 2-Me-4-NO2242 27 Me H H, 1 3-CF
3235 28 Me H H 1 3-I 216 29 Me H H 2 2-Me-4-OMe 205 30 Me H H 1 3-Br 230 31 Me H H 1 4-Ac 226 32 Me H H 1 4-Br 220 33 Me H H 1 4-CN 216 34 Me H H 1 3-NO
2242 35 Me H H, 1 4-Cl, 197 36 Me H H, 1 3-CH
3220 37 Me H H, 1 3-Cl, 209 38 Me H H 22,5-di-Me 204 39 Me H H 2 2-Me-6-OMe 223 40 Me H H2 22,3-di-Me 187 41 Me H H 1 2-OMe 192 42 Me H H 1 4-CO
2Et 202 43 Me H H 1 4-NMeAc 210 44 Me H H 22,6-di-Me＞250 45 Me H H, 1 2-(pyrroles-1-yl), 208 46 Me H H, 1 4-NO
2224 47 Me H H, 1 3-OCH
2Ph 214 48 Me H H 22,4-di-Me 213 49 Me H H 1 3-CN 200 50 Me H H 1 3-OCF
3＞250 51 Me H H 2 2-Me-3-NO
2233 52 Me H H, 1 2-OEt, 224 53 Me H H 1 4-(4-ClPhO), 224 54 Me H H, 1 4-CH
3248 55 Me H H 1 4-O-i-Pr 183 56 Me H H 1 4-F 247 57 Me H H 1 2-SMe 204 58 Me H H 1 2-t-Bu 248 59 Me H H 1 3-SMe 218 60 Me H H 1 4-OEt 195 61 Me H H 1 2-CH
2CN 191 62 Me H H 1 2-Et 200 63 i-Pr H 4-NO2/ 2 2-Me-4-Cl * * *
5-NO2
(1/1 mixes) 64 Me H 4-Br/, 2 2-Me-4-Cl * * *
5-Br
(1/1 mixes) 65 Me H H 1 2-CONH (i-Pr)-6-Me 248 66
*Me H H 2 2-Me-4-Cl * * * 67
*Me H H 2 2-Me-4-OCF
3* * 68 Me H H 2 2-Me-5-NO
2242 69 Me H H, 2 2-Me-4-CF
3250 70 Me H H, 1 4-CF
3246 71 Me H H 1 2-Ph, 163 72 Me H H, 2 2-(1-Me-tetrazolium-5-yl)-6-Me 202 73 Me H H 1 2-CONHMe 235 74 Me H H 2 2-Me-6-Cl 231 75 Me H H 2 3-NO
2-4-Me 22376 Me H H 3 2-F-4-Cl-5-NO
225077 Me H H, 2 2-Br-4-Me, 19878 Me H H, 3 2-Br-4,6-di-F 19779 Me H H 22,5-di-NO
222380 Me H H, 2 2-F-4-Cl, 25081 Me H H, 2 2-Me-3-F, 24282 Me H H 2 2-Br-4-F, 126.583 Me H H, 1 2-(morpholine-4-yl), 19384 Me H H, 2 3-NO
2-4-F 24885 Me H H 23,4-di-F 11086 Me H H 2 2-Cl-4-F 25087 Me H H 1 2-CF
321788 Me H H, 2 2-CN-4-Cl, 25089 Me H H, 1 2-Ac, 23790 Me H H, 1 2-OCF
320991 Me H H, 1 2-SCF
321192 Me H H, 2 2-CF
3-4-Br 250
*This sample contains 1 of 25 weight %, and 8-naphthalic anhydride * * * is referring to the NMR data of concordance list E
Concordance list B 
Compound R
2R
3R
4J fusing point ℃ 93 Me H H
199 compound Rs
2R
3R
4J fusing point ℃ 94 Me H H
175 95 Me H H
126.5 96 Me H H
217 97 Me H H
171
Concordance list C 
Compound R
2R
3R
4M R
5Fusing point ℃ 98 (Ex.2) i-Pr H H 23,4-di-F 227 99 i-Pr H H 22,3-di-Me 242 100 i-Pr H H 22,4-di-F 204 101 i-Pr H H 1 4-OCF
3186 102 i-pr H H, 1 4-Cl, 218 103 i-Pr H H, 1 4-Et, 206104 i-Pr H H, 1 4-CF
3165105 Me H H 23,4-di-F 250106 Me H H 22,3-di-Me 184.5107 Me H H 22,4-di-F 207108 Me H H 1 4-Cl 250109 Me H H 1 4-Et 250110 Me H H 1 4-CF
3208111 Me H H, 1 4-OCF
3144112 Me H H, 1 2-Me, 173.5113 i-pr H H, 1 2-Me, 176.5114 i-Pr H H, 2 2-Me-4-O-CF
3173.5115 i-Pr H H 2 2-Me-4-CF
3194.5116 Me H H 2 2-Me-4-OCF
3173.5117 Me H H 2 2-Me-4-CF
3204.5
Concordance list D 
Compound R
2R
3R
4J fusing point ℃ 118 i-Pr H H 1-naphthyl 210 119 i-Pr H H 2-thienyl 208120 (Ex.3) Me H H 2-thienyl 215 121 Me H H 1-naphthyl 214 121 i-Pr H H210 123 Me H H
210124 Me H H
215.5125 i-Pr H H
186
Concordance list E
Compound number
1
H NMR data (are CDCl
3
Solution, unless otherwise mentioned)
a
4?????????(DMSO-d6)δ：0.9(m，6H)，2.37(s，3H)，3.01(m?1H)，3.96(d，2H)、7.27-8.48(m，10H)，
9.84(br?s，1H).
5?????????(DMSO-d6)δ：2.36(s，3H)，2.88(s，3H)，2.94(s，3H)，7.28-8.08(m，10H)，9.99(s，1H).
(DMSO-d6)δ：1.07(t，3H)，2.37(s，3H)，3.22(m，2H)，7.30-8.06(m，9H)，8,40?(t，1H)，
9.86(s，1H).
10????????(DMSO-d6)δ：2.36(s，3H)，7.25-8.08(m，11H)，9.88(s，1H)，
63????????(DMSO-d6)δ：1.09(d，6H)，2.36(s，3H)，4.03(m，1H)，7.27-8.52(m，9H)，10.04(s，1H).
64????????(DMSO-d6)δ：2.36(s，3H)，2.69(d，3H)，7.33-8,84(r，8H)，8.45(br?q，1H)，9,98(s，1H)，
66????????(DMSO-d6)δ：2.37(s，3H)，2.71(d，3H)，7.27-8.10(m，9H)，8,34(br?q，1H)，9.88(s，1H).
67 (DMSO-d6) δ: 2.41 (s, 3H), 2.72 (d, 3H), 7.26-8.08 (m, 9H), 8,36 (br q, 1H), 9,95 (s, 1H).
A 1H NMR data unit is ppm, the tetramethylsilane downfield.Coupling is labeled as: (s) being singlet state (d) to be doublet, (t) is triplet state, (q) is quartet, (m) is multiplicity, (dd) is the doublet of doublet, (dt) is the doublet of triplet state, and (br s) is wide singlet state, and (bs q) is wide quartet.
Biological Examples of the present invention
Test A
In order to assess the control to meadow mythimna separata (Spodoptera frugiperda), testing apparatus is made up of little open containers, wherein is equipped with and places 4-5 days maize plant.Larva with 1 day age of 10-15 bar has carried out the insect infection in advance to this corn, larva is on a slice insect bait, with sampler from the sclerosis that many larvas are arranged grows thereon insect bait sheet pipette a pat, the sample that then this is contained larva and bait is transferred in the testing apparatus.The larva that moves on on the testing installation as the bait sample will become dry.
Unless otherwise mentioned, with the solution test preparation compound that contains following material: 10% acetone, the X-77_Spreader Lo-Foam Formula nonionic surface active agent of 90% water and 300ppm, this tensio-active agent contain alkylaryl polyoxyethylene, free fatty acids, two pure and mild Virahols (Loveland Industries, Inc.).Use the described preparation compound liquid of 1ml by the SUJ2 atomizing nozzle, this atomizing nozzle is positioned at each testing apparatus top 1.27cm (0.5 inch) to be located, and has the casing (Spraying System Co.) of 1/8 JJ customization.All experimental compounds in this shielding all spray with 250ppm, and repeat to spray 3 times.Behind the test compound that sprays described preparation, made each testing apparatus dry 1 hour, add a cover the black covering lid then atop.In 25 ℃, the growth chamber of 70% relative humidity, testing apparatus was placed 6 days.Estimate the plant damage degree of ingesting then.
In the compound of being tested, the following splendid plant protection degree (10% or the lower damage of ingesting) of having passed through: 1,7,11,16,48,66 and 67.
Test B
In order to assess the control to tobacco budworm (Heliothis virescens), testing apparatus is made up of little open containers, and the vegetable lamb of placing 6-7 days wherein is housed.Larva with 82 day ages has carried out the insect infection in advance to this cotton, and larva is on a slice insect bait, has used the described sampler as test A.
The preparation of test compound and spray all as described in the test A with 250ppm.Repeat to spray 3 times.After the sprinkling, testing apparatus is placed in the growth chamber, as described in test A, estimates evaluation then.
In the compound of being tested, the following splendid plant protection degree (10% or the lower damage of ingesting) of having passed through: 1,7 and 16.
Test C
In order to assess the control to diamond back moth (Plutella xylostella), testing apparatus is made up of little open containers, and the radish plant of placing 12-14 days wherein is housed.With 10-15 bar newborn larvae this radish has been carried out the insect infection in advance, larva is on a slice insect bait, has used the described sampler as test A.
The preparation of test compound and spray all as described in the test A with 250ppm.Repeat to spray 3 times.After the sprinkling, testing apparatus is placed in the growth chamber, as described in test A, estimates evaluation then.
In the compound of being tested, the following splendid plant protection degree (10% or the lower damage of ingesting) of having passed through: 1,7,11,12,14,16,20,24,37,48,51,54,55,56,61,66,67,69,70,72,75,81,85,86,89,90,91,93 and 97.
Test D
In order to assess the control to beet armyworm (Spodoptera exigua), testing apparatus is made up of little open containers, wherein is equipped with and places 4-5 days maize plant.Larva with 1 day age of 10-15 bar has carried out the insect infection in advance to this corn, and larva is on a slice insect bait, has used the described sampler as test A.
The preparation of test compound and spray all as described in the test A with 250ppm.Repeat to spray 3 times.After the sprinkling, testing apparatus is placed in the growth chamber, as described in test A, estimates evaluation then.
In the compound of being tested, the following splendid plant protection degree (10% or the lower damage of ingesting) of having passed through: 1,40 and 54.
Claims (17)
1. be selected from compound and N-oxide and the applicable salt of agricultural of following formula I or formula II:Wherein each J is benzyl ring, naphthyl member ring systems, 5 or 6 yuan of hetero-aromatic rings or fragrant 8,9 or 10 yuan of assorted dicyclo condensed ring systems independently, and wherein, each ring or member ring systems are randomly with 1-5 R5Replace; A and B are O or S independently; N is 0-4; R1H: or C1-C
6Alkyl, C2-C
6Alkenyl, C2-C
6Alkynyl or C3-C
6Cycloalkyl is randomly one or more following substituting group replacements that are selected from: halogen, CN, NO separately2, hydroxyl, C1-C
4Alkoxyl, C1-C
4Alkylthio, C1-C
4Alkyl sulfinyl, C1-C
4Alkyl sulphonyl, C2-C
4Alkoxy carbonyl, C1-C
4Alkyl amino, C2-C
8Dialkyl amido and C3-C
6Cycloalkyl amino; Perhaps R1C2-C
6Alkyl-carbonyl, C2-C
6Alkoxy carbonyl, C2-C
6Alkyl amino-carbonyl or C3-C
8Dialkyl amino carbonyl; R2H, C1-C
6Alkyl, C2-C
6Alkenyl, C2-C
6Alkynyl, C3-C
6Cycloalkyl, C1-C
4Alkoxyl, C1-C
4Alkyl amino, C2-C
8Dialkyl amido, C3-C
6Cycloalkyl amino, C2-
C
6Alkoxy carbonyl or C2-C
6Alkyl-carbonyl; R3H; Or C1-C
6Alkyl, C2-C
6Alkenyl, C2-C
6Alkynyl or C3-C
6Cycloalkyl is randomly one or more following substituting group replacements that are selected from: halogen, CN, NO separately2, hydroxyl, C1-C
4Alkoxyl, C1-C
4Alkylthio, C1-C
4Alkyl sulfinyl and C1-C
4Alkyl sulphonyl; Perhaps R2And R3Can form ring by the nitrogen that is connected with them, this ring contains 2-6 carbon atom and randomly contains other nitrogen, sulphur or an oxygen atom together, and this ring optionally is selected from C1-C
2Alkyl, halogen, CN, NO2And C1-C
2The 1-4 of alkoxyl substituting group replaces; With each R4With each R5H, C independently1-C
6Alkyl, C2-C
6Alkenyl, C2-C
6Alkynyl, C3-C
6Cycloalkyl, C1-C
6Haloalkyl, C2-C
6Halogenated alkenyl, C2-C
6Halo alkynyl, C3
-C
6Halogenated cycloalkyl, halogen, CN, CO2H、CONH
2、NO
2, hydroxyl, C1-C
4Alkoxyl, C1-C
4Halogenated alkoxy, C1-C
4Alkylthio, C1-C
4Alkyl sulfinyl, C1-C
4Alkyl sulphonyl, C1-C
4Haloalkyl thio, C1-C
4Haloalkyl sulfinyl, C1-C
4Halogenated alkyl sulfonyl, C2-C
4Alkoxy carbonyl, C1-C
4Alkyl amino, C2-C
8Dialkyl amido, C3
-C
6Cycloalkyl amino, C2-C
6Alkyl-carbonyl, C2-C
6Alkoxy carbonyl, C2-C
6Alkyl amino-carbonyl, C3-C
8Dialkyl amino carbonyl or C3-C
6Trialkylsilkl; Perhaps each R4With each R5Be phenyl, benzyl, phenoxy group, 5 or 6 yuan of hetero-aromatic rings or fragrant 8,9 or 10 yuan of assorted dicyclo condensed ring systems independently, each ring is randomly 1 or 3 and is independently selected from following substituting group replacement: C1-C
4Alkyl, C2-C
4Alkenyl, C2-C
4Alkynyl, C3-C
6Cycloalkyl, C1-C
4Haloalkyl, C2-C
4Halogenated alkenyl, C2-C
4Halo alkynyl, C3-C
6Halogenated cycloalkyl, halogen, CN, NO2、C
1-C
4Alkoxyl, C1-C
4Halogenated alkoxy, C1-C
4Alkylthio, C1-C
4Alkyl sulfinyl, C1-C
4Alkyl sulphonyl, C1-C
4Alkyl amino, C2-
C
8Dialkyl amido, C3-C
6Cycloalkyl amino, C3-C
6(alkyl) cycloalkyl amino, C2-C
4Alkyl-carbonyl, C2-C
6Alkoxy carbonyl, C2-C
6Alkyl amino-carbonyl, C3-C
8Dialkyl amino carbonyl or C3-C
6Trialkylsilkl; Perhaps (R5)
2Can be combined and become-OCF in the time of on being connected in adjacent carbon atom2O-、-CF
2CF
2O-or-OCF2CF
2O-。
2. the formula I compound of claim 1, wherein A and B are 0; R
1Be H, C
1-C
4Alkyl, C
2-C
4Alkenyl, C
2-C
4Alkynyl, C
3-C
6Cycloalkyl, C
2-C
6Alkyl-carbonyl or C
2-C
6Alkoxy carbonyl; With n be 0-2.
3. the formula II compound of claim 1, wherein A and B are 0; R
1Be H, C
1-C
4Alkyl, C
2-C
4Alkenyl, C
2-C
4Alkynyl, C
3-C
6Cycloalkyl, C
2-C
6Alkyl-carbonyl or C
2-C
6Alkoxy carbonyl; With n be 0-2.
4. claim 2 or 3 compound, wherein J is benzyl ring or 5 yuan or 6 yuan of hetero-aromatic rings that are selected from following J-1, J-2, J-3 and J-4, each J ring is randomly used 1-3 R
5Replace
Q is O, S or NR
5W, X, Y and Z are N or CR independently
5, prerequisite is that W, X, Y or Z are N one of at least in J-3 and J-4; R
2Be H, C
1-C
4Alkyl, C
2-C
4Alkenyl, C
2-C
4Alkynyl, C
3-C
6Cycloalkyl, C
2-C
6Alkyl-carbonyl or C
2-C
6Alkoxy carbonyl; R
3Be C
1-C
6Alkyl, C
2-C
6Alkenyl, C
2-C
6Alkynyl or C
3-C
6Cycloalkyl randomly is one or more following substituting group replacements that are selected from: halogen, CN, C separately
1-C
2Alkoxyl group, C
1-C
2Alkylthio, C
1-C
2Alkyl sulfinyl and C
1-C
2Alkyl sulphonyl; A R
4Group connects the naphthyl member ring systems at 2 or 7, and this R
4Be C
1-C
4Alkyl, C
1-C
4Haloalkyl, halogen, CN, NO
2, C
1-C
4Alkoxyl group, C
1-C
4Halogenated alkoxy, C
1-C
4Alkylthio, C
1-C
4Alkyl sulfinyl, C
1-C
4Alkyl sulphonyl, C
1-C
4Haloalkyl thio, C
1-C
4Haloalkyl sulfinyl or C
1-C
4Halogenated alkyl sulfonyl; Each R
5Be H, C independently
1-C
4Alkyl, C
1-C
4Haloalkyl, halogen, CN, NO
2, C
1-C
4Alkoxyl group, C
1-C
4Halogenated alkoxy, C
1-C
4Alkylthio, C
1-C
4Alkyl sulfinyl, C
1-C
4Alkyl sulphonyl, C
1-C
4Haloalkyl thio, C
1-C
4Haloalkyl sulfinyl, C
1-C
4Halogenated alkyl sulfonyl or C
2-C
4Alkoxy carbonyl, C
3-C
8Dialkyl amino carbonyl; Or each R
5Be phenyl, benzyl or 5 yuan or 6 yuan of hetero-aromatic rings independently, each ring randomly is that following substituting group replaces: C
1-C
4Alkyl, C
2-C
4Alkenyl, C
2-C
4Alkynyl, C
3-C
6Cycloalkyl, C
1-C
4Haloalkyl, C
2-C
4Halogenated alkenyl, C
2-C
4Halo alkynyl, C
3-C
6Halogenated cycloalkyl, halogen, CN, NO
2, C
1-C
4Alkoxyl group, C
1-C
4Halogenated alkoxy, C
1-C
4Alkylthio, C
1-C
4Alkyl sulfinyl, C
1-C
4Alkyl sulphonyl, C
1-C
4Alkylamino, C
2-C
8Dialkyl amido, C
3-C
6Cycloalkyl amino, C
3-C
6(alkyl) cycloalkyl amino, C
2-C
4Alkyl-carbonyl, C
2-C
6Alkoxy carbonyl, C
2-C
6Alkyl amino-carbonyl, C
3-C
8Dialkyl amino carbonyl or C
3-C
6Trialkylsilkl; Or (R
5)
2Can lump together when being connected with adjacent carbons becomes-OCF
2O-,-CF
2CF
2O-or-OCF
2CF
2O-; With n be 1-2.
5. the formula I compound of claim 4, wherein R
2Be H; R
3Be C
1-C
4Alkyl; With at least one R
5Substituting group and NR
1C (=B) part ortho position.
6. the compound of claim 5, wherein R
3It is methyl.
7. the formula II compound of claim 4, wherein R
1Be H or C
1-C
4Alkyl; R
2Be H or C
1-C
4Alkyl; R
3Be randomly to use halogen, CN, OCH
3Or S (O)
pCH
3The C that replaces
1-C
4Alkyl; A R
5Group with C (=B) NR
1The part adjacent links to each other with J on the position, and this R
5Be C
1-C
4Alkyl, C
1-C
4Haloalkyl, halogen, CN, NO
2, C
1-C
4Alkoxyl group, C
1-C
4Halogenated alkoxy, C
1-C
4Alkylthio, C
1-C
4Alkyl sulfinyl, C
1-C
4Alkyl sulphonyl, C
1-C
4Haloalkyl thio, C
1-C
4Haloalkyl sulfinyl, C
1-C
4Halogenated alkyl sulfonyl or C
2-C
4Alkoxy carbonyl; C
3-C
8Dialkyl amino carbonyl or phenyl, benzyl, or 5 yuan or 6 yuan of hetero-aromatic rings, each ring randomly are that following substituting group replaces: halogen, CN, NO
2, C
1-C
4Alkyl, C
2-C
4Alkenyl, C
2-C
4Alkynyl, C
3-C
6Cycloalkyl, C
1-C
4Haloalkyl, C
1-C
4Alkoxyl group or C
1-C
4Halogenated alkoxy; And the 2nd optional R
5Group is C independently
1-C
4Alkyl, C
1-C
4Haloalkyl, halogen, CN, NO
2, C
1-C
4Alkoxyl group, C
1-C
4Halogenated alkoxy, C
1-C
4Alkylthio, C
1-C
4Alkyl sulfinyl, C
1-C
4Alkyl sulphonyl, C
1-C
4Haloalkyl thio, C
1-C
4Haloalkyl sulfinyl, C
1-C
4Halogenated alkyl sulfonyl or C
2-C
4Alkoxy carbonyl; C
3-C
8Dialkyl amino carbonyl or phenyl, benzyl, or 5 yuan or 6 yuan of hetero-aromatic rings, each ring randomly are that following substituting group replaces: halogen, CN, NO
2, C
1-C
4Alkyl, C
2-C
4Alkenyl, C
2-C
4Alkynyl, C
3-C
6Cycloalkyl, C
1-C
4Haloalkyl, C
1-C
4Alkoxyl group or C
1-C
4Halogenated alkoxy.
7. the compound of claim 6, wherein J is phenyl, pyrazoles, pyrroles, pyridine or pyrimidine, each all by with C (=B) NR
1A R who links to each other with J on the part adjacent position
5With second optional R
5Replace.
8. the compound of claim 7, wherein R
1And R
2All are H; A R
4With NR
1C (=X) 7 of J part adjacent are gone up and are connected, and be selected from C
1-C
3Alkyl, CF
3, OCF
3, OCHF
2, S (O)
pCF
3, S (O)
pCHF
2And halogen, and the 2nd optional R
4With NR
1C (=X) 5 upward connections of J part contraposition, and be selected from halogen, C
1-C
3Alkyl and C
1-C
3Haloalkyl.
9. the compound of claim 8, wherein J is J-1; Q is NR
5aX is N or CH; Y is CH; Z is CR
5bR
5aBe to be selected from halogen, C with one or two
1-C
4Alkyl, C
1-C
4Haloalkyl or C
1-C
4Phenyl that halogenated alkoxy replaced or 2-pyridyl; And R
5bBe halogen or CF
3
10. the compound of claim 1 is selected from N-methyl-N '-(2-bromo-4-fluorophenyl)-1,8-naphthalene-two formyl, N-methyl 8-[(3,4-difluorophenyl) carbonylamino]-1-naphthoyl and N-methyl 8-[(2-thienyl) carbonylamino]-the 1-naphthoyl.
11. a composition that is used to prevent and treat invertebrate pests comprises at least a in the compound of claim 1 of biologic effective dose and tensio-active agent, solid diluent or the liquid diluent.
12. the composition of claim 11 also comprises at least a additional bioactive compounds or the reagent of significant quantity.
13. the composition of claim 12, wherein, at least a additional bioactive compounds or reagent are selected from one group of segmental appendage insect agent for killing being made up of pyrethroids, amino formate, neonicotinoids, neuronal sodium channel plugging agent, desinsection Macrolide, γ-An Jidingsuan (GABA) antagonist, sterilant urea and neotonin.
14. the composition of claim 12, wherein, at least a additional bioactive compounds or reagent are selected from following sterilant, nematocides, miticide or biological reagent: avermectin (abamectin), Ortho 12420, the pyrrole worm is clear, avermectin (avermectin), Ai Zhading, R-1582, bifenthrin, Bifenazate, Buprofezin, carbofuran, fluorine azoles worm is clear, UC 62644, Chlorpyrifos 94, chlorpyrifos_methyl, chromafenozide, clothianidin, cyhalothrin, β-cyhalothrin, (RS) cyhalothrin, λ-cyhalothrin, Cypermethrin, fly eradication amine, Deltamethrin kills mite sulphur and swells diazinon, TH-6040, the luxuriant ether of Rogor ， Evil, emamectin, 5a,6,9,9a-hexahydro-6,9-methano-2,4, esfenvalerate, ethiprole, fenothiocarb, ABG-6215, Fenvalerate, azoles mite ester is killed the chrysanthemum ester, sharp strength spy, flonicamid, flucythrinate, taufluvalinate, flufenoxuron, Dyfonate, RH 0345, fluorine bell urea, Provado oxadiazole worm, propylamine phosphorus, the fluorine third oxygen urea, Phosphothion, Halizan, acephatemet, methidathion, methomyl, Entocon ZR 515, methoxychlor, monocrotophos, Runner, WL 35651, Rimon, thioxamyl, one six zero five, methyl 1, permethrin, phorate, zolone, R-1504, phosphamidon, Aphox, Profenofos, pymetrozine, pyridalyl, pyriproxyfen, tubatoxin, SPINOSAD 105, second Toyodan, RH-5992, Teflubenzuron, tefluthrin, Terbufos, tetrachlorvinphos, thiacloprid, thiamethoxam, UC-51762, disosultap, tralomethrin, Trichlorphon and desinsection are grand, aldicarb, thioxamyl, Nemacur, U-36059, chinomethionate, G-23922, cyhexatin, Mitigan, Hooker HRS 16, Te Ben oxazole, fenazaquin, fenbutatin oxide, Fenvalerate, azoles mite ester, hexythiazox, propargite, pyridaben, tebufenpyrad, bacillus thuringiensis (Bacillusthuringiensis), the bacillus thuringiensis delta-endotoxin, baculovirus, and carnivorism bacterium, virus and fungi.
15. the composition of claim 14, wherein, at least a additional bioactive compounds or reagent are selected from: Cypermethrin, (RS) cyhalothrin, cyfloxylate, β-cyfloxylate, esfenvalerate is killed the chrysanthemum ester, tralomethrin, fenothicarb, methomyl, thioxamyl, UC-51762, clothianidin, Provado, thiacloprid ， oxadiazole worm, SPINOSAD 105, avermectin (abamectin), avermectin (avermectin), emamectin, 5a,6,9,9a-hexahydro-6,9-methano-2,4, ethiprole, sharp strength spy, flufenoxuron, the luxuriant ether of desinsection Long ， Evil, pyriproxyfen, pymetrozine, U-36059, bacillus thuringiensis, bacillus thuringiensis delta-endotoxin, and and entomophagous fungi.
16. a method of preventing and treating invertebrate pests comprises this invertebrate pests or its environment are contacted with the compound of the claim 1 of biologic effective dose or the composition of claim 11.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US24089000P | 2000-10-17 | 2000-10-17 | |
| US60/240,890 | 2000-10-17 | ||
| US32383301P | 2001-09-21 | 2001-09-21 | |
| US60/323,833 | 2001-09-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1429199A true CN1429199A (en) | 2003-07-09 |
Family
ID=26933807
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN01805190A Pending CN1429199A (en) | 2000-10-17 | 2001-10-11 | Insecticidal 1,8-naphthalenedicarboxamides |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1326827A2 (en) |
| JP (1) | JP2004511538A (en) |
| CN (1) | CN1429199A (en) |
| BR (1) | BR0107384A (en) |
| WO (1) | WO2002032856A2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101765589A (en) * | 2007-07-31 | 2010-06-30 | 拜尔农科股份有限公司 | fungicide n-cycloalkyl-n-bicyclic-carboxamide derivatives |
| CN114630825A (en) * | 2019-11-01 | 2022-06-14 | 先正达农作物保护股份公司 | Pesticidally active fused bicyclic heteroaromatic compounds |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE60226875D1 (en) * | 2001-08-15 | 2008-07-10 | Du Pont | ORTHOSUBSTITUTED ARYLAMIDES FOR COMBATING WIRELESS PESTS |
| MX2007002584A (en) | 2004-09-02 | 2007-09-07 | Genentech Inc | Pyridyl inhibitors of hedgehog signalling. |
| EP1961746B1 (en) * | 2005-12-15 | 2012-03-28 | Nihon Nohyaku Co., Ltd. | Phthalamide derivative, agricultural or horticultural pesticide, and use of the pesticide |
| CN102428957A (en) * | 2011-12-20 | 2012-05-02 | 湖北仙隆化工股份有限公司 | Compounded insecticidal composition |
| EP3643711A1 (en) * | 2018-10-24 | 2020-04-29 | Bayer Animal Health GmbH | New anthelmintic compounds |
| JPWO2021177334A1 (en) * | 2020-03-04 | 2021-09-10 | ||
| CN113214106B (en) * | 2021-06-22 | 2023-05-09 | 河南师范大学 | Method for efficiently synthesizing primary amide and N-methyl secondary amide compounds |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0346841A3 (en) * | 1988-06-16 | 1991-01-09 | Ciba-Geigy Ag | 1-aryl-naphthoic acid amide and microbicides containing these |
| TW515786B (en) * | 1997-11-25 | 2003-01-01 | Nihon Nohyaku Co Ltd | Phthalic acid diamide derivatives, agricultural and horticultural insecticides, and a method for application of the insecticides |
-
2001
- 2001-10-11 EP EP01987739A patent/EP1326827A2/en not_active Withdrawn
- 2001-10-11 JP JP2002536040A patent/JP2004511538A/en active Pending
- 2001-10-11 WO PCT/US2001/042632 patent/WO2002032856A2/en not_active Application Discontinuation
- 2001-10-11 CN CN01805190A patent/CN1429199A/en active Pending
- 2001-10-11 BR BR0107384-2A patent/BR0107384A/en not_active Application Discontinuation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101765589A (en) * | 2007-07-31 | 2010-06-30 | 拜尔农科股份有限公司 | fungicide n-cycloalkyl-n-bicyclic-carboxamide derivatives |
| CN102977028A (en) * | 2007-07-31 | 2013-03-20 | 拜尔农科股份公司 | Fungicide N-cycloalkyl-N-bicyclic-carboxamide derivatives |
| CN102977028B (en) * | 2007-07-31 | 2015-05-06 | 拜尔农科股份公司 | Fungicide N-cycloalkyl-N-bicyclic-carboxamide derivatives |
| CN114630825A (en) * | 2019-11-01 | 2022-06-14 | 先正达农作物保护股份公司 | Pesticidally active fused bicyclic heteroaromatic compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2002032856A3 (en) | 2002-07-04 |
| JP2004511538A (en) | 2004-04-15 |
| BR0107384A (en) | 2002-09-24 |
| WO2002032856A9 (en) | 2004-04-08 |
| EP1326827A2 (en) | 2003-07-16 |
| WO2002032856A2 (en) | 2002-04-25 |
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