Amidine compounds and herbicides

Information

  • Patent Application
  • 20110301355
  • Publication Number
    20110301355
  • Date Filed
    August 02, 2006
    18 years ago
  • Date Published
    December 08, 2011
    12 years ago
Abstract
Novel amidine compounds which may be active ingredients in herbicides that are reliably effective at a lesser dose and highly safe, and herbicides containing these compounds as active ingredients are provided. Amidine compounds represented by a formula (1′)
Description
FIELD OF THE INVENTION

The present invention relates to novel amidine compounds and herbicides which contain these compounds.


Priority is claimed on Japanese Patent Applications No. 2005-224452 and 2006-128341, filed Aug. 2, 2005 and May 2, 2006, respectively, the content of which is incorporated herein by reference.


BACKGROUND ART

Many herbicides are being used for weed control, which has required intensive labor in the past when growing field and garden crops. However, the development of drugs which are reliably effective at a lesser dose and which are also possible to use safely is desired due to the occurrence of chemical damage to crops, environmental persistence of the drugs, and environmental pollution caused by the drugs.


Regarding the present invention, non-patent document 1 describes the production method of N-aryl-N′ alkylcyanoformamidine similar to the compounds of the present invention.


However, this document does not describe that N-aryl-N′ alkylcyanoformamidine has herbicidal activity.

  • [non-patent document 1] J. Org. Chem., Vol. 58, 7001 (1993)


DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention

An objective of the present invention is to provide novel amidine compounds which may be active ingredients of herbicides that are reliably effective when used in a low dose and are highly safe, and to provide herbicides which contain these compounds as active ingredients.


Means for Solving the Problem

As a result of intensive research in order to solve the abovementioned problem, the present inventors discovered that amidine compounds represented by the below formula (1) have an excellent herbicide activity to complete the present invention. In other words, the present invention firstly provides herbicides characterized by containing at least one kind of amidine compound represented by a formula (1).




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[In the formula, G is an optionally substituted nitrogen-containing heterocyclic group represented by a formula (2).




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Q represents cyano, optionally substituted iminoalkyl, optionally substituted amide, optionally substituted thioamide, or an optionally substituted nitrogen-containing heterocyclic group represented by a formula (3).




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(In the formula, a dotted line represents a single or a double bond which connects carbon and nitrogen atoms), and


A represents an optionally substituted aromatic group].


In the herbicides of the present invention, the formula (2) in the formula (1) is preferably a nitrogen-containing heterocyclic group which is 3 to 8-membered, saturated or unsaturated, and optionally substituted and more preferably an optionally substituted azetidine-1-yl group or an optionally substituted pyrrolidine-1-yl group.


In the herbicides of the present invention, in the formula (1), A is preferably a compound having an optionally substituted aromatic hydrocarbon group, and more preferably a compound having a group represented by a formula (4).




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In the formula, X represents halogen, optionally substituted C1-6 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted aryl, optionally substituted C1-6 alkyl carbonyl, optionally substituted C2-6 alkenyl carbonyl, optionally substituted C2-6 alkynyl carbonyl, optionally substituted aryl carbonyl, optionally substituted C1-6 alkylthiocarbonyl, optionally substituted C2-6 alkenylthiocarbonyl, optionally substituted C2-6 alkynylthiocarbonyl, optionally substituted arylthiocarbonyl, cyano, substitutent represented by X11, optionally substituted amino, nitro, hydroxyl, optionally substituted C1-6 alkoxy, optionally substituted C2-6 alkenyloxy, optionally substituted C2-6 alkynyloxy, optionally substituted aryloxy, optionally substituted heteroyloxy, mercapto, optionally substituted C1-6 alkylthio, optionally substituted C2-6 alkenylthio, optionally substituted C2-6 alkynylthio, optionally substituted arylthio, optionally substituted heteroylthio, optionally substituted alkyl sulfinyl, optionally substituted aryl sulfinyl, optionally substituted alkyl sulfonyl, optionally aryl sulfonyl, or optionally substituted heterocycle.


Moreover, substitutents which are in positions such that they are bondable to each other may bond together to form rings.


Here, the number of carbons present in the aforementioned substitutents with the phrase “optionally substituted” (i.e. C1-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, C1-6 alkylcarbonyl, C2-6 alkenylcarbonyl, C2-6 alkynylcarbonyl, C1-6 alkylthiocarbonyl, C2-6 alkenylthiocarbonyl, C2-6 alkynylthiocarbonyl, C1-6 alkoxy, C2-6 alkenyloxy, C2-6 alkynyloxy, C1-6 alkylthio, C2-6 alkenylthio, and C2-6 alkynylthio) refers to the number of carbons present in the groups without any substituents (i.e. alkyl, alkenyl, alkynyl, alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, alkylthiocarbonyl, alkenylthiocarbonyl, alkynylthiocarbonyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkenylthio, and alkynylthio). Hereinafter, the same applies.


n is an integer of 0 to 5. When n is 2 or more, each X may be the same or different from each other.


X11 is a substituent represented by a formula (5).




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wherein m1 represents an integer of 0 to 3; A1 represents an atom selected from carbon, nitrogen, oxygen, and sulfur, and which may be oxidized within a chemically acceptable range and which may be substituted; when m1 is 2 or more, each A1 may be the same or different from each other and combinations of each A1 are within a chemically acceptable range and each A1 may, within a chemically acceptable range of multiplicity, bond to each other.


When A1 is carbon and one or more A1 is substituted by two or more substitutents, the substituents which are in a bondable positional relationship may bond together to form a ring.


Z1 represents a group represented by —OR11 or —NR12R13.


R11 represents hydrogen, optionally substituted C1-6 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted aryl, optionally substituted heterocycle, or a group represented by X12.


R12 and R13 each independently represents hydrogen, optionally substituted C1-6 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted aryl, optionally substituted heterocycle, a group represented by X12, hydroxyl, optionally substituted C1-6 alkoxy, optionally substituted C2-6 alkenyloxy, optionally substituted C2-6 alkynyloxy, optionally substituted aryloxy, optionally substituted alkyl sulfinyl, optionally substituted aryl sulfonyl, optionally substituted alkyl sulfonyl, optionally substituted aryl sulfonyl, or optionally substituted amino.


Moreover, these groups may form covalent bonds or, within a chemically acceptable range, may faun ionic bonds.


Furthermore, R12 and R13 may bond together to form a ring.


X12 is a substituent represented by a formula (6).




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[In the formula, m2 is an integer of 1 to 3, A2 represents optionally substituted carbon and may be substituted within a chemically acceptable range. When m2 is 2 or more, each A2 may bond to each other within a chemically acceptable range of multiplicity.


When one or more A2 is substituted by two or more substituents, the substituents which are in a bondable positional relationship may bond together to form a ring.


Y represents oxygen or optionally substituted nitrogen.


Z2 is a group represented by —OR21 or —NR22R23 when Y is oxygen and Z2 represents hydrogen or optionally substituted C1-6 alkyl when Y is nitrogen.


R21 represents hydrogen, optionally substituted C1-6 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted aryl, optionally substituted heterocycle, or a group represented by X13.


R22 and R23 each independently represents hydrogen, optionally substituted C1-6 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted aryl, optionally substituted heterocycle, a group represented by X13, optionally substituted C1-6 alkoxy, optionally substituted C2-6 alkenyloxy, optionally substituted C2-6 alkynyloxy, optionally substituted aryloxy, optionally substituted alkyl sulfinyl, optionally substituted aryl sulfinyl, optionally substituted alkyl sulfonyl, or optionally substituted aryl sulfonyl.


Moreover, these groups may form covalent bonds or, within a chemically acceptable range, may form ionic bonds.


Furthermore, R22 and R23 may bond together to form a ring when neither is hydrogen.


X13 is a substituent represented by a formula (7).




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(In the formula, m3 is an integer of 1 to 3, A3 represents optionally substituted carbon and may be substituted within a chemically acceptable range. When m3 is 2 or more, each A3 may bond to each other within a chemically acceptable range of multiplicity.


When one or more A3 is substituted by two or more substituents, the substituents which are in a bondable positional relationship may bond together to form a ring.


Z3 is a group represented by —OR31 or —NR32R33.


R31 represents hydrogen, optionally substituted C1-6 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted aryl, or optionally substituted heterocycle.


R32 and R33 each independently represents hydrogen, optionally substituted C1-6 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted C1-6 alkoxy, optionally substituted C2-6 alkenyloxy, optionally substituted C2-6 alkynyloxy, optionally substituted aryloxy, optionally substituted alkyl sulfinyl, optionally substituted aryl sulfinyl, optionally substituted alkyl sulfonyl, or optionally substituted aryl sulfonyl.


Moreover, these groups may form covalent bonds or, within a chemically acceptable range, may form ionic bonds.


Furthermore, R32 and R33 may bond together to form a ring when neither is hydrogen.


Secondly, the present invention provides amidine compounds represented by a formula (1′).




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{In the formula, G′ represents an optionally substituted nitrogen-containing heterocyclic group represented by a formula (2′)




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with a proviso that the number of carbons constituting the nitrogen-containing heterocycle of the nitrogen-containing heterocyclic group is 10 or less and that 2H-Indazole ring is excluded.


Q′ represents cyano, optionally substituted iminoalkyl, optionally substituted amide, optionally substituted thioamide, or optionally substituted and condensed 5-membered ring group represented by a formula (3′).




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A′ is a group represented by a formula (4′).




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[In the formula, X represents halogen, optionally substituted C1-6 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted aryl, optionally substituted C1-6 alkyl carbonyl, optionally substituted C2-6 alkenyl carbonyl, optionally substituted C2-6 alkynyl carbonyl, optionally substituted aryl carbonyl, optionally substituted C1-6 alkylthiocarbonyl, optionally substituted C2-6 alkenylthiocarbonyl, optionally substituted C2-6 alkynylthiocarbonyl, optionally substituted arylthiocarbonyl, cyano, substitutent represented by X11, optionally substituted amino, nitro, hydroxyl, optionally substituted C1-6 alkoxy, optionally substituted C2-6 alkenyloxy, optionally substituted C2-6 alkynyloxy, optionally substituted aryloxy, optionally substituted heteroyloxy, mercapto, optionally substituted C1-6 alkylthio, optionally substituted C2-6 alkenylthio, optionally substituted C2-6 alkynylthio, optionally substituted arylthio, optionally substituted heteroylthio, optionally substituted alkyl sulfinyl, optionally substituted aryl sulfinyl, optionally alkyl sulfonyl, optionally substituted aryl sulfonyl, or an optionally substituted heterocyclic group.


Moreover, substitutents which are in positions such that they are bondable to each other may bond together to form rings.


n′ is an integer of 2 to 5. Each X may be the same or different from each other.


X11 is a substituent represented by a formula (5).




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[In the formula, m1 represents an integer of 0 to 3; A1 represents an atom selected from carbon, nitrogen, oxygen, and sulfur, and which may be oxidized within a chemically acceptable range and which may be substituted; when m1 is 2 or more, each A1 may be the same or different from each other and combinations of each A1 are within a chemically acceptable range and each A1 may, within a chemically acceptable range of multiplicity, bond to each other.


When A1 is carbon and one or more A1 is substituted by two or more substitutents, the substituents which are in a bondable positional relationship may bond together to form a ring.


Z1 represents a group represented by —OR11 or —NR12R13.


R11 represents hydrogen, optionally substituted C1-6 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted aryl, optionally substituted heterocycle, or a group represented by X12.


R12 and R13 each independently represents hydrogen, optionally substituted C1-6 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted aryl, optionally substituted heterocycle, a group represented by X12, hydroxyl, optionally substituted C1-6 alkoxy, optionally substituted C2-6 alkenyloxy, optionally substituted C2-6 alkynyloxy, optionally substituted aryloxy, optionally substituted alkyl sulfinyl, optionally substituted aryl sulfinyl, optionally substituted alkyl sulfonyl, optionally substituted aryl sulfonyl, or optionally substituted amino.


Moreover, R12 and R13 may bond together to form a ring.


X12 is a substituent represented by a formula (6).




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[In the formula, m2 is an integer of 1 to 3, A2 represents optionally substituted carbon and may be substituted within a chemically acceptable range. When m2 is 2 or more, each A2 may bond to each other within a chemically acceptable range of multiplicity. When one or more A2 is substituted by two or more substituents, the substituents which are in a bondable positional relationship may bond together to form a ring.


Y represents oxygen or optionally substituted nitrogen.


Z2 is a group represented by —OR21 or —NR22R23 when Y is oxygen and Z2 represents hydrogen or optionally substituted C1-6 alkyl when Y is nitrogen.


R21 represents hydrogen, optionally substituted C1-6 allyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted aryl, optionally substituted heterocycle, or a group represented by X13.


R22 and R23 each independently represent hydrogen, optionally substituted C1-6 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted aryl, optionally substituted heterocycle, a group represented by X13, optionally substituted C1-6 alkoxy, optionally substituted C2-6 alkenyloxy, optionally substituted C2-6 alkynyloxy, optionally substituted aryloxy, optionally substituted alkyl sulfinyl, optionally substituted aryl sulfinyl, optionally substituted alkyl sulfonyl, or optionally substituted aryl sulfonyl. Moreover, R22 and R23 may bond together to form a ring when neither is hydrogen.


X13 is a substituent represented by a formula (7).




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(In the formula, m3 is an integer of 1 to 3, A3 represents optionally substituted carbon and may be substituted within a chemically acceptable range. When m3 is 2 or more, each A3 may bond to each other within a chemically acceptable range of multiplicity.


When one or more A3 is substituted by two or more substituents, the substituents which are in a bondable positional relationship may bond together to form a ring.


Z3 is a group represented by —OR31 or —NR32R33.


R31 represents hydrogen, optionally substituted C1-6 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted aryl, or an optionally substituted heterocyclic group.


R32 and R33 each independently represents hydrogen, optionally substituted C1-6 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted aryl, optionally substituted heterocycle, optionally substituted C1-6 alkoxy, optionally substituted C2-6 alkenyloxy, optionally substituted C2-6 alkynyloxy, optionally substituted aryloxy, optionally substituted allyl sulfinyl, optionally substituted aryl sulfinyl, optionally substituted alkyl sulfonyl, or optionally substituted aryl sulfonyl.


Moreover, R32 and R33 may bond together to form a ring when neither is hydrogen.)]]]}


In the amidine compounds of the present invention, formula (2′) in the formula (1′) is preferably a nitrogen-containing heterocycle which is 3 to 8-membered, saturated or unsaturated, and optionally substituted; and more preferably optionally substituted azetidine-1-yl group or optionally substituted pyrrolidine-1-yl group.


Effects of the Invention

According to the present invention, novel amidine compounds and herbicides containing these compounds as active ingredients are provided.







PREFERRED EMBODIMENTS OF THE INVENTION

The present invention will be described in detail below.


The present invention is a herbicide characterized by containing one or more amidine compounds represented by the formula (1) and the novel amidine compounds represented by the formula (1′).


(1) Amidine Compounds Represented by Formulae (1) and (1′)

In the amidine compounds represented by the formula (1) (hereinafter referred to as the “compound (1)” at times), G is a group represented by the formula (2) (hereinafter referred to as the “nitrogen-containing heterocyclic group (2)”).


The nitrogen-containing heterocycle in the nitrogen-containing heterocyclic group (2) is a heterocycle having one or more nitrogen in the ring and which is saturated or non-saturated. The nitrogen-containing heterocycle may contain oxygen and/or sulfur in addition to nitrogen and may be monocyclic or may have a condensed ring structure or a crosslinked structure.


The total number of nitrogen, oxygen, and sulfur constituting the nitrogen-containing heterocycle is normally 1 to 4 and preferably 1 to 3.


Moreover, the number of carbons constituting the nitrogen-containing heterocycle of the nitrogen-containing heterocyclic group (2) is preferably 10 or less and more preferably 1 to 8.


Although specific examples of the nitrogen-containing heterocyclic group (2) include those shown in Table 1 below, it is not limited to them. Note that the substituents on nitrogen and on atoms constituting the ring are abbreviated and only the basic backbone is described here.












TABLE 1











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The substituents of the nitrogen-containing heterocyclic group (2) are not particularly limited.


For example, halogen such as fluorine, chlorine, and bromine; C1-6 alkyl which may have a substituent such as methyl, ethyl, trifluoromethyl, and benzyl; C2-6 alkenyl which may have a substituent such as aryl or 3-chloroaryl; C2-6 alkynyl which may have a substituent such as propargyl; aryl which may have a substituent such as phenyl or 4-methylphenyl; formyl;


C1-6 alkylcarbonyl which may have a substituent such as acetyl, or trifluoroacetyl; C2-6 alkenylcarbonyl which may have a substituent such as cinnamyl; C2-6 alkynylcarbonyl which may have a substituent such as propargylcarbonyl; aryl carbonyl which may have a substituent such as benzoyl or 4-chlorobenzoyl; C1-6 alkylthiocarbonyl which may have a substituent such as thioacetyl; C2-6 alkenylthiocarbonyl which may have a substituent such as allylthiocarbonyl; C2-6 alkynylthiocarbonyl which may have a substituent such as propargylthiocarbonyl; arylthiocarbonyl which may have a substituent such as thiobenzoyl; carboxyl; C1-6 alkoxycarbonyl which may have a substituent such as methoxycarbonyl or ethoxycarbonyl; C2-6 alkenyloxycarbonyl which may have a substituent such as acryloyl or methacryloyl;


C3-6 alkynyloxycarbonyl which may have a substituent such as propargyloxycarbonyl; aryloxycarbonyl which may have a substituent such as phenyoxycarbonyl or 2,4-dichlorophenoxycarbonyl; cyano; amino which may have a substituent such as amino, dimethylamino, or acetylamino; imino which may have a substituent such as imino or dimethylimino; nitro; hydroxyl; oxo; C1-6 alkoxy which may have a substituent such as methoxy, ethoxy, t-butoxy; C2-6 alkenyloxy which may have a substituent such as allyloxy or crotyloxy; C2-6 alkynyloxy which may have a substituent such as propargyloxy; aryloxy which may have a substituent such as phenoxy or 4-methylphenoxy; heteroyloxy which may have a substituent; mercapto; C1-6 alkylthio which may have a substituent such as methylthio or ethylthio; C2-6 alkenylthio which may have a substituent such as allylthio or crotylthio; C2-6 alkynylthio which may have a substituent such as propargylthio; arylthio which may have a substituent such as phenylthio; heteroylthio which may have a substituent; alkylsulfinyl which may have a substituent such as methylsulfinyl; arylsulfinyl which may have a substituent such as phenylsulfinyl; alkylsulfonyl which may have a substituent such as methylsulfonyl; arylsulfonyl which may have a substituent such as phenylsulfonyl; and a heterocyclic group which may have a substituent.


In addition, heterocycle of heteroyloxy group which may have a substituent, of heteroylthio group which may have a substituent, of a heterocycle group which may have a substituent includes cyclic compounds having at least one atom selected from nitrogen, oxygen and sulfur in the ring and which is saturated or unsaturated. Specific examples include aromatic heterocycles such as imidazole, pyrazole, pyridine, pyrimidine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, thiazole, oxazole, benzoimidazole, benzoxazole, benzothiazole, indolenine, tetrazaindene, and furan; and non-aromatic heterocycles such as pyrrolidine, piperidine, morpholine, tetrahydrofuran, tetrahydropyran, aziridine, azetidine, oxazolidine, piperazine, thiazolidine, and trioxane.


Moreover, the nitrogen-containing heterocyclic group (2) may have a plurality of the same or different substituents at arbitrary positions.


Q represents cyano, iminoalkyl which may have a substituent, amide which may have a substituent, thioamide which may have a substituent, or a nitrogen-containing heterocyclic group represented by the formula (3) and which may have a substituent.


Examples of iminoalkyl which may have a substituent include C1-6 iminoalkyl iminomethyl, iminoethyl, and iminopropyl.


Examples of iminoalkyl which may have a substituent include N-substituted iminomethyl where nitrogen is substituted by hydroxyl, by C1-6 alkoxy which may have a substituent, by C2-6 alkenyloxy which may have a substituent, by C2-6 alkynyloxy which may have a substituent, by aryloxy which may have a substituent, or by heteroyloxy which may have a substituent.


Examples of amide which may have a substituent include aminocarbonyl where 0 to 2 nitrogens are substituted by the group such as C1-6 alkyl which may have a substituent, C2-6 alkenyl which may have a substituent, C2-6 alkynyl which may have a substituent, aryl which may have a substituent, a heterocyclic group which may have a substituent, C2-10 acyl which may have a substituent, C2-6 alkenylcarbonyl which may have a substituent, C2-6 alkynylcarbonyl which may have a substituent, arylcarbonyl which may have a substituent, and heteroylcarbonyl which may have a substituent. Additionally, when 2 nitrogens are substituted, the substituents on nitrogen may bond to foam a ring structure within a chemically acceptable range.


Specific examples of thioamide which may have a substituent include aminothiocarbonyl where 0 to 2 nitrogens are substituted by a group such as C1-6 alkyl which may have a substituent, C2-6 alkenyl which may have a substituent, C2-6 alkynyl which may have a substituent, aryl which may have a substituent, a heterocyclic group which may have a substituent, C2-10 acyl which may have a substituent, C2-6 alkenylcarbonyl which may have a substituent, C2-6 alkynylcarbonyl which may have a substituent, arylcarbonyl which may have a substituent, and heteroylcarbonyl which may have a substituent. Additionally, when 2 nitrogens are substituted, the substituents on nitrogen may bond to form a ring structure within a chemically acceptable range.


In the group represented by the formula (3) (hereinafter referred to as the “nitrogen-containing heterocyclic group (3)” at times), the dotted line represents a single or double bond linking carbon and nitrogen. In other words, the nitrogen-containing heterocylic group (3) is one where the atom adjacent to the carbon having linkages is always nitrogen and these carbon and nitrogen link by a single or double bond, and also, having 1 to 4 nitrogens in the ring and which is saturated or unsaturated.


The nitrogen-containing heterocyclic group (3) may contain oxygen and/or sulfur in addition to nitrogen. The total number of nitrogen, oxygen, and sulfur constituting the heterocycle is normally 1 to 4 and preferably 1 to 3.


Moreover, although the number of members constituting the nitrogen-containing heterocycle of the nitrogen-containing heterocyclic group (3) is not particularly limited, it is normally 3 to 10 and preferably 3 to 8.


Although specific examples of the nitrogen-containing heterocyclic group (3) include imidazolyl, pyrazolyl, morpholynyl, triazolyl, indolyl, oxadiazolyl, quinolyl, oxazolyl, and those described in Table 2 below, it is not limited to them. Note that in Table 2 below, the substituents on nitrogen and on atoms constituting the ring are abbreviated and only the basic backbone is described.


[Table 2]












TABLE 2











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The substituent of the nitrogen-containing heterocyclic group (3) is not particularly limited and examples thereof include substituents similar to those shown as examples of the nitrogen-containing heterocyclic group (2).


Moreover, the nitrogen-containing heterocyclic group (3) may have a plurality of the same or different substituents at arbitrary positions.


A represents an aromatic group which may have a substituent.


Examples of the aromatic group of A include aromatic hydrocarbon groups such as phenyl, 1-naphthyl, or 2-naphthyl; and aromatic heterocyclic groups such as pyridyl, thiazole, or oxazole.


Among them, phenyl, which may have a substituent, is preferable as A and the group represented by a formula (4) is more preferable.


Specific examples of a formula (5), which is a substituent of the formula (4), include substituents shown below. The formula (5) below includes those containing formulae (6) and (7).




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Moreover, examples of the substituent of the functional group in X of the formula (4) include substituents similar to those shown as specific examples of the nitrogen-containing heterocyclic group (2).


The substituent of R11, R12, and R13 in Z1 is not particularly limited and examples thereof include substituents similar to those shown as specific examples of the nitrogen-containing heterocyclic group (2).


In the formula (6), Y represents oxygen or optionally substituted nitrogen and specifically represents NR101, NNR102NR103, NOR104, NS(═O)R105, NS(═O)2R106, or the like.


R101 to R106 each independently represents hydrogen, optionally substituted C1-6 alkyl, optionally substituted C1-6 alkyl carbonyl, optionally substituted C1-6 alkylthiocarbonyl, optionally substituted C1-6 alkoxycarbonyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkenyl carbonyl, optionally substituted C2-6 alkenylthiocarbonyl, optionally substituted C2-6 alkenyloxycarbonyl, optionally substituted C2-6 alkynyl, optionally substituted C2-6 alkynyl carbonyl, optionally substituted C2-6 alkynylthiocarbonyl, optionally substituted C2-6 alkynyloxycarbonyl, optionally substituted aryl, optionally substituted aryl carbonyl, optionally substituted arylthiocarbonyl, optionally substituted aryloxycarbonyl, optionally substituted heterocycle, optionally substituted heteroylcarbonyl, optionally substituted heteroylthiocarbonyl, optionally substituted heteroyloxycarbonyl, and the substituent substituting these groups is not particularly limited and examples thereof include those similar to the substituent of nitrogen-containing heterocyclic group (2).


Among them, in the present invention, A is preferably the group represented by the formula (4) from the viewpoint of providing excellent herbicide activity, and more preferably 2,4-di-substituted phenyl, 4,5-disubstituted phenyl, or 2,4,5-trisubstituted phenyl, and most preferably 2,4,5-trisubstituted phenyl.


Additionally, although geometric isomerism in imino linkages is not particularly limited, the substituents A and G are preferably transisomers.


The compound (1) can be produced by the production method 1 to 7 shown below, for example. Note that unless particularly shown clearly in the figures below, reaction stereospecificity does not exist.


(Production Method 1)

The compound (1) can be produced by the method described in the literature below.


J. Org. Chem., Vol. 58, 7001 (1993), etc.




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(In the formula, A is as defined above.)


A compound (8), which is a raw material for the production, can be produced by the method described in the literature (R. Appel et al., Chem. Ber., Vol. 118, 1632 (1985)).


(Production Method 2)

The compound (1a) can also be produced by the method shown below.




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(In the formula, A is as defined above.)


Examples of halogenating agents used in the halogenating reaction of a compound (13) include CCl4—PPh3, CBr4—PPh3, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, thionyl chloride, sulfuryl chloride, chlorine, phosphorus oxybromide, thionyl bromide, and bromine.


The amount of halogenating agent is used normally 1 to 5 times that of the compound (13), which is the substrate, in terms of moles.


The reaction using such a halogenating agent can be carried out in an appropriate inert solvent.


The inert solvent to be used is not particularly limited as long as it is inert solvent in the reaction. Examples include, for instance, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and 1,2-dichloroethane; aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as pentane, hexane, and octane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; ethers such as diethylether and tetrahydrofuran; amides such as N,N-dimethylformamide and N-methylpyrolidone; sulfoxides such as dimethylsulfoxide; nitriles such as acetonitrile; and mixed solvents of two or more kinds thereof.


Although the reaction temperature is not particularly limited, the temperature range is normally from 0° C. to the boiling point of the solvent used.


After the completion of the reaction using a halogenating agent, it is preferable to react cyano compounds after removing the excess halogenating agent from the reaction system.


Examples of cyano compounds to be used include, for instance, metal cyanides such as cuprous cyanide, potassium cyanide, and sodium cyanide.


The amount of cyano compounds used is normally 1 to 5 times that of the compound (13), which is the substrate, in teens of mole.


The reaction using cyano compounds can be carried out in an appropriate inert solvent.


Examples of the inert solvent to be used include those similar to the abovementioned listed solvents which can be used in the reaction using a halogenating agent.


Although the reaction temperature is not particularly limited, the temperature range is normally from 0° C. to the boiling point of the solvent used.


(Production Method 3)

The compound (1a) can also be produced by the method shown below.




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(In the formula, A is as defined above. R represents alkyl and E represents a leaving group.)


The compound represented by R-E to be reacted with the compound (15) is an alkylating agent, and examples thereof include, for instance, alkyl halides such as methyl iodide and dialkyl sulfates such as dimethyl sulfate.


Examples of the bases used here include metal hydroxides such as sodium hydroxide and potassium hydroxide; carbonates such as sodium carbonate and potassium carbonate; metal hydrides such as sodium hydride; metal alkoxides such as sodium methoxide and sodium ethoxide; and organic bases such as triethylamine and pyridine.


The reaction of the compound (15) with the compound represented by the formula R-E can be carried out in an appropriate inert solvent.


The inert solvent to be used is not particularly limited as long as it is an inert solvent in the reaction. Examples include, for instance, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and 1,2-dichloroethane; aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as pentane, hexane, and octane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; ethers such as diethylether and tetrahydrofuran; ketones such as acetone and methylethylketone; amides such as N,N-dimethylformamide; and mixed solvents of two or more kinds thereof.


Although the reaction temperature is not particularly limited, the temperature range is normally from 0° C. to the boiling point of the solvent used.


Examples of the cyano compounds to be reacted with the compound (16) include those similar to the cyano compounds listed in the Production method 2 which can be suitably used.


In addition, the usage of the cyano compounds, solvents, or the like to be used are also similar to those in the Production method 2.


(Production Method 4)

The compound (1a) can also be produced by the method shown below.




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(In the formula, A is as defined above.)


Examples of cyano compounds, halogenating agents, and the compound (11) which can be used here include ones similar to those listed in the Production method 2. Moreover, the cyano compounds, halogenating agents and the usage of the compound (11), and solvents to be used, or the like, are also similar to those in the Production method 2.


(Production Method 5)

A compound (1b) whose Q is amide (CONH2) in the formula (1) (hereinafter referred to as the “compound (1b)”) and a compound (1c) whose Q is a substituted amide (CONr1r2) in the formula (1) (hereinafter referred to as the “compound (1c)”) can be produced by the method shown below.




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(In the formula, A is as defined above r1 and r2 each independently represents hydrogen, alkyl, aryl, or acyl with a proviso that r1 and r2 are not hydrogen.)


The reaction to obtain the compound (1b) by hydrolyzing the compound (1a) can be carried out similarly to a known reaction method to obtain amides by hydrolyzing cyanos.


Examples of the reaction method to obtain the compound (1c) from the compound (1b) include, for instance, a method of applying alkylating agents such as methyl iodide and dimethyl sulfate to the compound (1b) in the presence of a base; or a method of applying acylating agents such as acetylchloride and benzoylchloride to the compound (1b) in the presence of a base.


(Production Method 6)

A compound (1d) whose Q is thioamide in the formula (1) and a compound (1e) whose Q is a substituted thioamide in the formula (1) can be produced by the method shown below.




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(In the formula, A, r1 and r2 are defined as above.)


The reaction to obtain the compound (1d) from the compound (1a) can be carried out similarly to a known reaction method which converts cyanos to thioamides by applying hydrogen sulfide.


Moreover, the reaction to obtain the compound (1e) from the compound (1d) can be carried out similarly to the method to obtain the compound (1c) from the compound (1b) in the Production method 5.


(Production Method 7)

A compound (1f) can also be produced by the method shown below.




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(In the formula, Q and A are defined as above.)


Specific examples of halogenating agents and the compound (11) used here, the usages thereof, reaction conditions, or the like, are similar to those described above in Production method 2.


Examples of salts of the compound (1) include the salts obtained from the compound (1) and acids.


Specific examples of the salts of the compound (1) include salts of inorganic acids such as hydrochlorides, nitrates, sulfates, and phosphates; and salts of organic acids such as acetates, lactates, benzoates, and salicylates.


The production method of salts of the compound (1) is not particularly limited and examples thereof include a conventionally known production method such as the method of mixing/stirring the compound (1) with a predetermined amount of acid in an appropriate solvent.


In all cases, targeted compounds can be isolated in high yield after completing the reaction by an after-treatment operation, purification operation, or the like following common procedures in synthetic organic chemistry


Structures of targeted compounds can be identified by measurements of IR spectra, NMR spectra, and mass spectra, elemental analysis, or the like.


Note that although geometric isomers, or the like, may exist in the compound (1) due to the double bond between carbon and nitrogen, these isomers are all within the scope of the present invention.


The compound (1) obtained as described above has an excellent herbicidal activity, as described later, and is useful as an active ingredient of herbicides.


(2) Herbicide

Herbicides of the present invention are characterized by containing at least one kind of the compound (1) or salts thereof (hereinafter referred to as the “compound of the present invention”),as an active ingredient.


The compounds of the present invention exhibit high herbicidal activity in either soil treatment or foliar treatment under upland farming conditions; are effective on various upland weeds such as crabgrass, giant foxtail, velvetleaf, and pigweed; and also include compounds which exhibit selectivity toward crops such as corn.


Moreover, the compounds of the present invention include compounds which exhibit plant growth-regulating activity such as retarding and defoliant toward useful plants such as agricultural crops, ornamental plants, and fruit trees.


Additionally, the compounds of the present invention include compounds which have excellent exhibit herbicidal activity on various lowland weeds and which exhibit selectivity toward rice.


Furthermore, the compounds of the present invention can also be applied for controlling weeds in such places as fruit farms, lawns, railway track margins, and vacant lands.


The compounds of the present invention can be used in pure form without adding any other components when applied practically, and also can be used, with an objective to use as agrochemicals, in the form which general agrochemicals may adopt, that is, wettable powder, granules, dusting powder, emulsifiable concentrates, water-soluble powder, suspending agent, flowable, or the like.


As additives and carriers, vegetable powders such as soy flour and wheat flour; fine mineral powder such as diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, and clay; and organic and inorganic compounds such as sodium benzoate, urea, and sodium sulfate are used when solid formulation is required.


When a liquid formulation is required, petroleum fractions such as kerosene, xylene, and solvent naphtha, and cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alcohol, acetone, trichloroethylene, methyl isobutyl ketone, mineral oil, vegetable oil, water, or the like, are used as a solvent.


Additionally, in order to achieve homogenous and stable foams in these formulations, it is also possible to add surfactants if necessary.


Although surfactants are not particularly limited, examples thereof include, for instance, nonionic surfactants such as alkylphenyl ether where polyoxyethylene is added, alkyl ether where polyoxyethylene is added, higher fatty acid ester where polyoxyethylene is added, sorbitan higher fatty acid ester where polyoxyethylene is added, and tristyryl phenyl ether where polyoxyethylene is added; sulfate ester of alkyl phenyl ether where polyoxyethylene is added, alkyl naphthalene sulfonate, polycarboxylate, lignin sulfonate, formaldehyde condensate of alkyl naphthalene sulfonate, and isobutylene-maleic anhydride copolymer.


Although concentrations of active ingredients in herbicides of the present invention vary depending on the aforementioned forms of formulation, in wettable powder for instance, the concentration of 5 to 90 weight % (hereinafter written simply as “%”) and preferably 10 to 85% is used; 3 to 70% and preferably 5 to 60% is used in emulsion; and 0.01 to 50% and preferably 0.05 to 40% is used in granules.


Wettable powder and emulsifiable concentrate obtained in this way, which are diluted to predetermined concentrations by water, are sprayed or mixed in soil as emulsion solution or suspension solution before or after the weed germination. When herbicides of the present invention are practically used, an adequate amount of active ingredients, which is 0.1 g or more per 1 hectare, is applied.


Herbicides of the present invention can also be used by mixing with known fungicides, insecticides, acaricides, other herbicides, plant growth regulators, fertilizers, or the like. In addition, not only labor saving but also a further higher effect can be expected due to synergism with mixed chemicals. In this case, combined use with a two or more of known herbicides is also possible.


Chemicals suitable to be mixed and used with the herbicides of the present invention include anilide herbicides such as diflufenican, picolinafen, and propanil; chloroacetanilide herbicides such as alachlor and pretilachlor; aryloxyalkanoic acid herbicides such as 2,4-D and 2,4-DB; aryloxyphenoxyalkanoic acid herbicides such as diclofop-methyl and fenoxaprop-ethyl; cyclohexanedione herbicides such as sethoxydim and tralkoxydim; carboxylic acid herbicides such as dicamba and picloram; imidazolinone herbicides such as imazaquin and imazethapyr; urea herbicides such as diuron and isoproturon; carbamate herbicides such as chlorpropham and phenmedipham; thiocarbamate herbicides such as thiobencarb and EPTC; dinitroaniline herbicides such as trifluralin and pendimethalin; diphenyl ether herbicides such as acifluorfen and fomesafen; sulfonylurea herbicides such as bensulfuron-methyl and nicosulfuron; pyrimidinyl carboxy herbicides such as pyrithiobac and bispyribac; triazinone herbicides such as metribuzin and metamitron; triazine herbicides such as atrazine and cyanazine; uracil herbicides such as bromacil and lenacil; triazolopyrimidine herbicides such as flumetsulam and penoxsulam; nitrile herbicides such as bromoxynil and dichlobenil; phosphate herbicides such as glyphosate and glufosinate; bipyridilium herbicides such as paraquat and diquat; cyclic imide herbicides such as flumioxazin, flumiclorac-pentyl, and fluthiacet-methyl; benzoylaminopropionate herbicides such as benzoylprop ethyl and furamprop ethyl;


other herbicides such as MSMA, asulam, chloridazon, norflurazon, flurtamone, fluorochloridone, flucarbazone-sodium, propoxycarbazone-sodium, amicarbazone, isoxaben, flupoxam, quinclorac, quinmerac, diflufenzopyr-sodium, oxadiazon, oxadiargyl, piperophos, daimuron, bentazone, benfuresate, ethofumesate, difenzoquat, naproanilide, triazofenamide, clomazone, sulcotrione, mesotrione, pyrasulfotole, isoxaflutole, isoxachlortole, topramezone, dithiopyr, thiazopyr, amitrole, pyrazoxyfen, pylazolynate, benzobicyclon, pyridate, pyridafol, azafenidin, carfentrazone-ethyl, sulfentrazone, pentoxazone, pyraflufen-ethyl, fluazolate, flufenpyr-ethyl, butafenacil, pyraclonil, bencarbazone, cinmethylin, oxaziclomefone, dimethenamide, fentrazamide, indanofan, cafenstrole, pyributycarb, pyrimisulfan, pinoxaden, and KIH-485 (test name).


Moreover, it is also possible to add additives such as vegetable oils and oil concentrates to the composition, which are combined with the above herbicides.


EXAMPLE

Although the present invention will be described further in detail next by use of examples, the scope of the present invention is not limited in any way by the examples below. It should be noted that compound number described below is corresponding to the chemical number in Table 3 below.


Example 1
Production of N′-(2,4-dichlorophenyl)-N,N-(butane-1,4-di-yl)cyanoformamidine (compound 1-1: compound number 178)

4,5-Dichloro-1,2,3-dithiazolium chloride was synthesized by the method described in the literature (Appel, R. et al., Chem. Ber., Vol. 118, 1632 (1985)). By reacting 13.40 g of the obtained 4,5-dichloro-1,2,3-dithiazolium chloride with 10.43 g of 2,4-dichloroaniline with the method described in the above literature, 13.66 g of 4-chloro-5-[(2,4-dichlorophenyl)imino]-5H-1,2,3-dithiazol was obtained (yield 71%).


By reacting 0.50 g of this 4-chloro-5-[(2,4-dichlorophenyl)imino]-5H-1,2,3-dithiazol with 0.37 g of pyrrolidine following the method described in the literature (J. Org. Chem., Vol. 58, 7001 (1993)), 0.20 g of N′-(2,4-dichlorophenyl)-N,N-(butane-1,4-di-yl)cyanoformamidine (1-1) was obtained (yield: 44%).


ηD20.7 1.6158


Example 2
Production of N′-(2,4-dichlorophenyl)-N,N-(butane-1,4-di-yl)cyanoformamidine (compound 1-1: compound number 178)

3.76 g of 2,4-dichlorophenyl isocyanate was dissolved in 100 ml of benzene and 1.44 g of pyrrolidine was added to this resulting solution and reacted for 8 hours at room temperature. After completing the reaction, benzene was evaporated under reduced pressure to obtain 5.19 g of N-(2,4-dichlorophenyl)pyrrolidine-1-carboxamide. 0.50 g of the obtained N-(2,4-dichlorophenyl)pyrrolidine-1-carboxamide was dissolved in the mixed solvent composed of 10 ml of acetonitrile and 0.4 ml of carbon tetrachloride and 0.69 g of triphenylphosphine was then added to this resulting solution and the entire mixture was stirred for 1 hour at room temperature. 0.55 g of cuprous cyanide was added to this reaction solution and the entire mixture was refluxed for 2.5 hours. After cooling the reaction solution, insolubles were removed by filtration and the concentrate obtained by evaporating the filtrate under reduced pressure was purified by silica gel column chromatography to obtain 0.39 g of N′-(2,4-dichlorophenyl)-N,N-(butane-1,4-di-yl)cyanoformamidine (1-1) (yield: 72%).


Example 3
Production of N′-(4-chloro-2-fluoro-5-propargyloxyphenyl)-N,N-(butane-1,4-di-yl)cyanoformamidine (compound 1-2: compound number 141)

0.30 g of 4-chloro-2-fluoro-5-propargyloxyphenyl isothiocyanate was dissolved in 5 ml of acetonitrile and 0.09 g of pyrrolidine was then added to this and stirred for 0.5 hours at room temperature. 0.17 g of potassium carbonate and subsequently 0.19 g of methyl iodide were added to this resulting solution and refluxed for 1 hour. After cooling, insolubles were separated by filtration and the resulting filtrate was evaporated under reduced pressure to obtain 0.38 g of N′-(4-chloro-2-fluoro-5-propargyloxyphenyl)-N,N-(butane-1,4-di-yl)methylthioformamide. 0.05 g of N′-(4-chloro-2-fluoro-5-propargyloxyphenyl)-N,N-(butane-1,4-di-yl)methylthioformamide was dissolved in 1 ml of dimethylformamide and 0.02 g of potassium cyanide was then added to the resulting solution and reacted for 5 hours at 60 to 80° C. The resultant solution was purified by preparative thin layer chromatography (PTLC) to obtain 0.02 g of N′-(4-chloro-2-fluoro-5-propargyloxyphenyl)-N,N-(butane-1,4-di-yl)cyanoformamidine (1-2). Yield was 47%. m.p. 88-89° C.


Example 4
Production of N′-(2,4-dichlorophenyl)-N,N-(butane-1,4-di-yl)cyanoformamidine (compound 1-1: compound number 178)

40 ml of acetonitrile solution containing 6.44 g of 2,4-dichlorophenyl isothiocyanate was added dropwise to 40 ml of aqueous solution containing 2.28 g of potassium cyanide at 0° C. over 1 hour. After 3 hours of reaction at room temperature, the reaction solution was poured into a mixed solution of 50 ml of 1N hydrochloric acid and ice. Deposited crystals were separated by filtration and were dried under reduced pressure to obtain 7.14 g of N-(2,4-dichlorophenyl)cyanothioformamide (yield: 97%).


0.50 g of N-(2,4-dichlorophenyl)cyanothioformamide was dissolved in 25 ml of benzene and after adding 0.51 g of phosphorus pentachloride, the resultant solution was refluxed for 2 hours. The reaction solution was vacuum-concentrated and the concentrate was dissolved in 30 ml of acetonitrile, and after the addition of 0.63 g of pyrrolidine at 0° C., reacted for 1.5 hours at room temperature. The concentrate obtained by vacuum concentration of the resulting reaction solution was purified by silica gel column chromatography to obtain 0.08 g of N′-(2,4-dichlorophenyl)-N,N-(butane-1,4-di-yl)cyanoformamidine (1-1) (yield: 13%).


Example 5
Production of 2-[2,4-dichloro-5-(1-ethoxycarbonylethoxy)phenylimino]-2-(pyrrolidine-1-yl)acetamide (compound 1-3: compound number 293)

Apart from the use of 2,4-dichloro-5-hydroxyaniline instead of 2,4-dichloroaniline, N′-(2,4-dichloro-5-hydroxyphenyl)-N,N-(butane-1,4-di-yl)cyanoformamidine was obtained by the same manner to that in Example 1. 3.22 g of N′-(2,4-dichloro-5-hydroxyphenyl)-N,N-(butane-1,4-di-yl)cyanoformamidine was dissolved in 30 ml of diethyl ether and 30 ml of 10% sodium hydroxide solution was then added and the resulting solution was stirred for 1 hour at room temperature. The aqueous layer was separated and after adding concentrated hydrochloric acid thereto with cooling by ice-water, benzene was added resulting in the deposition of white solid matter. By removing crystals by filtration, 2.53 g of 2-(2,4-dichloro-5-hydroxyphenylimino)-2-(pyrrolidine-1-yl)acetamide was obtained (yield 83%).


0.5 g of the obtained 2-(2,4-dichloro-5-hydroxyphenylimino)-2-(pyrrolidine-1-yl)acetamide was dissolved in 50 ml of acetonitrile and 0.25 g of potassium carbonate was then added and the entire mixture was heated to reflux for 1 hour. 0.37 g of ethyl 2-bromopropionate was added to the resulting reaction solution and further heated to reflux for 1 hour. Insolubles were removed from the resultant reaction solution by filtration and the concentrate obtained by evaporating solvents from the filtrate by evaporation under reduced pressure was purified by silica gel column chromatography to obtain 0.37 g of 2-[2,4-dichloro-5-(1-ethoxycarbonylethoxy)phenylimino]-2-(pyrrolidine-1-yl)acetamide (1-3) (yield 55%). m.p. 160-163° C.


Example 6
Production of 1-ethoxy-2-methyl-1-oxopropane-2-yl-5-(2-acetamide-1-(pyrrolidine-1-yl)-2-thioxoethylideneamino)-2-chloro-4-fluorobenzoate (compound 1-4: compound number 201)

Apart from the use of 2-fluoro-4-chloro-5-(1-ethoxycarbonyl-1-methylethoxycarbonyl)aniline instead of 2,4-dichloroaniline, 1-ethoxy-2-methyl-1-oxopropane-2-yl-2-chloro-5-[cyano(pyrrolidine-1-yl)methyleneamino]-4-fluorobenzoate was obtained by the same manner to that in Example 1. 1.95 g of 1-ethoxy-2-methyl-1-oxopropane-2-yl-2-chloro-5-[cyano(pyrrolidine-1-yl)methyleneamino]-4-fluorobenzoate was dissolved in a mixture of 3 ml of pyridine and 0.48 g of triethylamine and hydrogen sulfide was then introduced to the resulting solution at room temperature. After verifying the completion of the reaction by thin layer chromatography, the reaction solution was poured into ice-cold water and extracted with ethyl acetate. The organic layer was washed with saturated saline and dried with anhydrous magnesium sulfate. 2.06 g of a crude product of 1-ethoxy-2-methyl-1-oxopropane-2-yl-5-(2-amino-1-(pyrrolidine-1-yl)-2-thioxoethylideneamino)-2-chloro-4-fluorobenzoate was obtained by evaporating solvents under reduced pressure.


0.23 g of the obtained 1-ethoxy-2-methyl-1-oxopropane-2-yl-5-(2-amino-1-(pyrrolidine-1-yl)-2-thioxoethylideneamino)-2-chloro-4-fluorobenzoate was dissolved in 10 ml of acetone and after the addition of 0.09 g of pyridine, a solution of 5 ml of acetone containing 0.09 g of acetylchloride was added dropwise thereto at room temperature over 20 minutes. After refluxing the reaction solution for 2 hours, the resulting solution was poured into ice-cold water and extracted with chloroform. The organic layer was washed with saturated saline, dried with anhydrous magnesium sulfate, and filtered. The concentrate obtained by evaporating solvents from the filtrate under reduced pressure was purified by silica gel column chromatography to obtain 0.06 g of 1-ethoxy-2-methyl-1-oxopropane-2-yl-5-(2-acetamide-1-(pyrrolidine-1-yl)-2-thioxoethylideneamino)-2-chloro-4-fluorobenzoate (1-4) (yield 23%). Amorphous.


Example 7
Production of 2-(4-chloro-2-fluoro-5-propargyloxyphenylimino)-2-(pyrrolidine-1-yl)acetaldehyde O-methyloxime (compound 1-5: compound number 190)

6 ml of aqueous solution containing 4.19 g of O-methylhydroxylamine hydrochloride was added to 6 ml of aqueous solution containing 4.67 g of glyoxylic acid monohydrate. 5 ml of aqueous solution containing 2.0 g of sodium hydroxide was added dropwise to the obtained solution under ice-cooling and after the addition, the resulting solution was stirred at room temperature for 1.5 hours. The resultant reacting solution was extracted by the addition of ethyl acetate. After washing with saturated saline, the organic layer was dried with anhydrous magnesium sulfate and filtered. 4.62 g of 2-(methoxyimino)acetate was obtained by evaporating solvents from the filtrate under reduced pressure (yield 89%).


0.58 g of the obtained 2-(methoxyimino)acetate was dissolved in 30 ml of xylene and 1.00 g of 4-chloro-2-fluoro-5-propargyloxyaniline was added thereto. 0.17 ml of phosphorus trichloride was then added to the resulting solution and the entire mixture was heated to reflux for 1 hour. After cooling the resulting reaction solution, sodium bicarbonate water was added thereto and the resultant solution was then extracted with ethyl acetate. After washing with saturated saline, the organic layer was dried with anhydrous magnesium sulfate and filtered. The concentrate obtained by evaporating solvents from the filtrate under reduced pressure was washed with a mixed solvent of ether-normal hexane to obtain 0.70 g of N-(4-chloro-2-fluoro-5-propargyloxyphenyl)-2-(methoxyimino)acetamide (yield 49%).


0.42 g of the obtained N-(4-chloro-2-fluoro-5-propargyloxyphenyl)-2-(methoxyimino)acetamide was dissolved in 30 ml of benzene and after the addition of 0.36 g of phosphorus pentachloride, the resulting solution was refluxed for 4 hours. The concentrate obtained by concentrating the resulting reaction solution under reduced pressure was dissolved in 20 ml of dichloromethane and 0.32 g of pyrrolidine was added dropwise thereto at room temperature and the resultant solution was stirred at room temperature for 1 hour. The concentrate obtained by evaporating solvents from the resulting reaction solution under reduced pressure was purified by silica gel column chromatography to obtain 0.32 g of 2-(4-chloro-2-fluoro-5-propargyloxyphenylimino)-2-(pyrrolidine-1-yl)acetaldehyde O-methyloxime (1-5) (yield 64%). m.p. 73-75° C.


Example 8
Production of N′-(4-chloro-2-fluoro-5-propargyloxyphenyl)-N,N-(butane-1,4-di-yl)-4,5-dihydroisooxazole-3-carboxyamidine (compound 1-6: compound number 207)

0.63 g of 4,5-dihydroisooxazole-3-carboxylic acid was dissolved in 40 ml of dichloromethane and then 0.66 ml of oxalyl chloride and subsequently a catalytic amount of N,N-dimethylformamide were added thereto at room temperature and the entire mixture was stirred at room temperature for 45 minutes. 0.77 g of 4,5-dihydroisooxazole-3-carboxylic acid chloride was obtained by evaporating solvents from the resulting reaction solution under reduced pressure.


On the other hand, 1.00 g of 4-chloro-2-fluoro-5-propargyloxyaniline was dissolved in 30 ml of dichloromethane and 0.53 g of pyridine was added thereto. 20 ml of dichloromethane solution containing 0.77 g of 4,5-dihydroisooxazole-3-carboxylic acid chloride, which was obtained beforehand, was then added dropwise to the resulting solution with ice-cooling over 10 minutes and after the addition was completed, the resultant solution was stirred at room temperature for 2 hours. The organic layer was separated from the resulting reaction solution, sequentially washed with 1N hydrochloric acid, 10% sodium bicarbonate water, and saturated saline, dried with anhydrous magnesium sulfate, and then filtered. The concentrate obtained by evaporating solvents from the filtrate under reduced pressure was washed with a mixed solvent of ether-normal hexane to obtain 1.43 g of N-(4-chloro-2-fluoro-5-propargyloxyphenyl)-4,5-dihydroisooxazole-3-carboxyamide (yield 88%).


1.27 g of the obtained N-(4-chloro-2-fluoro-5-propargyloxyphenyl)-4,5-dihydroisooxazole-3-carboxyamide was reacted with phosphorus pentachloride and subsequently with pyrrolidine in the same manner as that in Example 7 to obtain 1.42 g of N′-(4-chloro-2-fluoro-5-propargyloxyphenyl)-N,N-(butane-1,4-di-yl)-4,5-dihydroisooxazole-3-carboxyamidine (1-6) (yield 94%). m.p. 79-81° C.


Specific examples of the compound (1) produced as described so far are shown in Table 3 below.


In Table 3, when there is a description in the section of physical constant “132-133”, for example, it shows that the melting temperature (° C.) is between 132° C. and 133° C. Likewise, “22.4° C. 1.5928” shows a refractive index at 22.4° C., “amorphous” shows an amorphous state, and “viscous oil” shows a viscous-oil state.


In addition, abbreviations of substituents used in Table 3 are those as shown in Tables below showing examples of chemical formulae and substituents.




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Substituent (N, O, S, heterocycle)










No.
Structural formula







N001


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N002


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N003


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N004


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N005


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N006


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N007


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S001


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S002
—S—C≡C—CH3







S003


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S004
—S—COCH3







S005


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S006


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S007


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S008
—S—CH2—C≡CH







S009


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T001


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T002
—O—CH2CH≡CH2



T003
—O—CH2—C≡CH



T004
—O—CH2—CBr≡CH2







T005


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T006


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T007
—O—CF═CF—CH═CH2







T008


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T009


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T010


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T011


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T012


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T013


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T014


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T015


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T016


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T017


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T018
—O—CH2—O—CH3







T019


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T020


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T021


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T022
—O—CH2CH3



T023
—O—CH2CH2CH3



T024
—O—CH2CH2CH2CH3







T025


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T026
—O—CH2—C≡CSi(CH3)3







T027


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T028


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T029


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T030


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T031


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T032


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T033


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T034


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T035


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T036


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T037


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T038


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T039


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T040


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T041


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T042


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T043


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T044


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T045
—O—CH3







T046


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T047


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T048


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T049


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T050


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T051


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T052


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T053


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T054


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T055


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T056


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T057


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T058


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T059


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T060


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T061


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T062


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T063


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T064


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T065


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T066


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T067


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T068


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T069


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T070


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T071


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T072


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T073


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T074


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T075


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T076


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T077


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T078


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T079


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T080


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H001


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H002


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H003


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H004


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H005


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H006


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H007


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H008


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H009


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H010


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H011


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H012


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H013


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H014


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H015


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H016


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H017


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H018


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C001


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C002


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C003


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Substituent (X11)













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No.
(A1)m1
Z1
(A2)m2
Y
Z2
(A3)m3
Z3





X101
m1 = 0
—OH







X102
m1 = 0
—OCH3







X103
m1 = 0
—OC2H5










X104
m1 = 0


embedded image












X105
m1 = 0
—OCH2—CH═CH2










X106
m1 = 0


embedded image












X107
m1 = 0


embedded image












X108
m1 = 0


embedded image












X109
m1 = 0


embedded image












X110
m1 = 0


embedded image












X111
m1 = 0


embedded image












X112
m1 = 0


embedded image












X113
m1 = 0


embedded image












X114
m1 = 0


embedded image












X115
m1 = 0


embedded image












X116
m1 = 0


embedded image












X117
m1 = 0


embedded image












X118
m1 = 0


embedded image












X119
m1 = 0


embedded image












X120
m1 = 0


embedded image












X121
m1 = 0


embedded image












X122
—CH2—CHCl—
—OC2H5







X123
—CH═CCl—
—OC2H5










X124


embedded image


—OC2H5










X125
—NH—


embedded image












X126
—NH—


embedded image












X127


embedded image




embedded image












X128
—NH—CH2
—OC2H5







X129
—O—CH2
—OH







X130
—O—CH2
—OC2H5










X131
—O—CH2


embedded image












X132
—O—CH2
—OCH2—C≡CH










X133
—O—CH2


embedded image












X134
—O—CH2


embedded image












X135


embedded image


—OCH3










X136


embedded image


—OC2H5










X137


embedded image


—OH










X138


embedded image


—OC2H5










X139


embedded image




embedded image












X140


embedded image




embedded image












X141


embedded image


—OCH3










X142
—S—CH2
—OC2H5










X143
—S—CH2


embedded image












X144
—S—CH2
—OCH2—CH═CH2










X145


embedded image


—OCH3










X146


embedded image


—OC2H5










X147
—O—CH2—


embedded image












X148
m1 = 0


embedded image












X149
m1 = 0
—OCH2—C≡CH







X150
m1 = 0
—OCH2—C2F5







X151
m1 = 0
—NH—C2H5







X152
m1 = 0
—OCH2CF3







X153
m1 = 0
—OCH(CF3)2







X201
m1 = 0
—OX12
—CH2
O
—OC2H5







X202
m1 = 0
—OX12


embedded image


O
—OC2H5







X203
m1 = 0
—OX12


embedded image


O


embedded image









X204
m1 = 0
—OX12


embedded image


O
—OC2H5







X205
m1 = 0
—OX12


embedded image


O
—OC2H5







X206
m1 = 0
—OX12


embedded image


O
—OH







X207
m1 = 0
—O—X12


embedded image


O
—OCH3







X208
m1 = 0
—OX12


embedded image


0
—OC2H5







X209
m1 = 0
—OX12


embedded image


0


embedded image









X210
m1 = 0
—OX12


embedded image


0
—OCH2—CH═CH2







X211
m1 = 0
—NHX12


embedded image


0
—OC2H5







X212
m1 = 0
—OX12


embedded image


0
—NH2







X213
m1 = 0
—OX12


embedded image


0


embedded image









X214
m1 = 0
—OX12


embedded image


0


embedded image









X215
m1 = 0
—OX12


embedded image


0


embedded image









X216
m1 = 0
—OX12


embedded image


0


embedded image









X217
m1 = 0
—OX12


embedded image


0


embedded image









X218
m1 = 0
—OX12


embedded image


0


embedded image









X219
m1 = 0
—OX12


embedded image


0


embedded image









X220
m1 = 0
—OX12


embedded image


0


embedded image









X221
m1 = 0
—OX12


embedded image


0


embedded image









X222
m1 = 0
—OX12


embedded image


0


embedded image









X223
m1 = 0
—OX12


embedded image


0


embedded image









X224
m1 = 0
—OX12


embedded image


0


embedded image









X225
m1 = 0
—OX12


embedded image


0


embedded image









X226
m1 = 0
—OX12


embedded image


0


embedded image









X227
m1 = 0
—OX12


embedded image


0


embedded image









X228
m1 = 0
—OX12


embedded image


0


embedded image









X229
m1 = 0
—OX12


embedded image


0


embedded image









X230
m1 = 0
—OX12


embedded image


0


embedded image









X231
m1 = 0
—OX12


embedded image


0


embedded image









X232
m1 = 0
—OX12


embedded image


0


embedded image









X233
m1 = 0
—OX12


embedded image


0


embedded image









X234
m1 = 0
—OX12


embedded image


0
—H







X235
m1 = 0
—OX12


embedded image


0
—CH3







X236
m1 = 0
—OX12


embedded image


0
—C2H5







X237
m1 = 0
—OX12


embedded image


0
—CH2SCH3







X238
m1 = 0
—OX12


embedded image


0


embedded image









X239
m1 = 0
—OX12


embedded image


NOH
—H







X240
m1 = 0
—OX12


embedded image


NOCH3
—H







X241
m1 = 0
—OX12


embedded image


NOC2H5
—CH3







X242
m1 = 0
—OX12


embedded image


NOCH2—CH═CHCl
—H







X243
m1 = 0
—OX12


embedded image


NNHCOOC2H5
—H







X244
m1 = 0
—OX12


embedded image


0
—OH







X245
m1 = 0
—OX12


embedded image


0
—OC2H5







X246
m1 = 0
—OX12


embedded image


0


embedded image









X247
m1 = 0
—OX12


embedded image


0


embedded image









X248
m1 = 0
—OX12


embedded image


0
—OH







X249
m1 = 0
—OX12


embedded image


0
—OC2H5







X250
m1 = 0
—OX12


embedded image


0


embedded image









X251
m1 = 0
—OX12


embedded image


0


embedded image









X252
m1 = 0
—OX12


embedded image


0
—OH







X253
m1 = 0
—OX12


embedded image


0
—OC2H5







X254
m1 = 0
—OX12


embedded image


0


embedded image









X255
m1 = 0
—OX12


embedded image


0


embedded image









X256
m1 = 0
—OX12


embedded image


0
—OH







X257
m1 = 0
—OX12


embedded image


0
—OC2H5







X258
m1 = 0
—OX12


embedded image


0


embedded image









X259
m1 = 0
—OX12


embedded image


0


embedded image









X260
m1 = 0
—OX12


embedded image


0
—OH







X261
m1 = 0
—OX12


embedded image


0
—OC2H5







X262
m1 = 0
—NHX12


embedded image


O
—OCH3







X263
m1 = 0
—NHX12


embedded image


O
—OCH3







X264
m1 = 0
—NHX12


embedded image


O
—OCH2C6H5







X265
m1 = 0
—OX12


embedded image


O
—OCH2C2F5







X266
m1 = 0
—OX12


embedded image


O
—OCH(CF3)2







X267
m1 = 0
—OX12


embedded image


O
—OCH2CF3







X268
m1 = 0
—OX12


embedded image


O
—NHCH2CF3







X302
m1 = 0
—OX12


embedded image


O


embedded image


—CH2
—OC2H5





X303


embedded image




embedded image












X304


embedded image




embedded image












X305
m = 0
—OX12


embedded image


O


embedded image









X306
m = 0


embedded image












X307
m = 0
—OX12


embedded image


O


embedded image









X308
m = 0


embedded image












X309
m = 0


embedded image












X310
m = 0
—OX12


embedded image


O


embedded image









X311
m = 0


embedded image












X312
m = 0


embedded image












X313
m = 0


embedded image












X314
m = 0


embedded image












X315
m = 0


embedded image












X316
m = 0


embedded image












X317
m = 0


embedded image












X318
m = 0


embedded image












X319
m = 0


embedded image












X320
m = 0
—OX12


embedded image


O


embedded image









X321
m = 0


embedded image












X322
m = 0


embedded image












X323
m = 0


embedded image












X324
m = 0


embedded image































TABLE 3





No.
G
Q
X1
X2
X3
X4
X5
Physical constant























1


embedded image


—CN
—F
—H
—Cl
X208
—H
20.5° C. 1.5346





2


embedded image


—CN
—F
—H
—Cl
X210
—H
20.3° C. 1.5468





3


embedded image


—CN
—F
—H
—Cl
T003
—H
99-100





4


embedded image


—CN
—F
—H
—Cl
T003
—H
132-133





5


embedded image


—CN
—F
—H
—Cl
T003
—H
101-103





6


embedded image


—CN
—H
—H
—CN
X112
—H
22.4° C. 1.5928





7


embedded image


—CN
—H
—H
—CN
X226
—H
22.1° C. 1.5525





8


embedded image


—CN
—H
—H
—Cl
X123
—H
22.5° C. 1.577





9


embedded image


—CN
—H
—H
—Cl
X210
—H
22.5° C. 1.5506





10


embedded image


—CN
—H
—H
—Cl
X102
—H
20.6° C. 1.6026





11


embedded image


—CN
—F
—H
—CN
X208
—H
126-128





12


embedded image


—CN
—F
—H
—CN
X226
—H
AMORPHOUS





13


embedded image


—CN
—F
—H
—Cl
N001
—H
118-120





14


embedded image


—CN
—F
—H
—CN
T003
—H
113-115





15


embedded image


—CN
—F
—H
—OCHF2
—H
—H
22.4° C. 1.5376





16


embedded image


—CN
—F
—H
—OCHF2
X226
—H
22.1° C. 1.5329





17


embedded image


—CN
—F
—H
—OCHF2
X208
—H
22.3° C. 1.5055





18


embedded image


—CN
—F
—H
T008
—H
—H
108-110





19


embedded image


—CN
—F
—H
T009
—H
—H
81-83





20


embedded image


—CN
—F
—H
—Cl
—H
—H
20.6° C. 1.5959





21


embedded image


—CN
—F
—H
—Cl
—CH2OH
—H
23° C. 1.5786





22


embedded image


—CN
—F
—H
—Cl
X101
—H
166-169





23


embedded image


—CN
—F
—H
—Cl
X103
—H
22.8° C. 1.5426





24


embedded image


—CN
—F
—H
—Cl
X104
—H
20.8° C. 1.571





25


embedded image


—CN
—F
—H
—Cl
X105
—H
22.5° C. 1.5631





26


embedded image


—CN
—F
—H
—Cl
X106
—H
23.1° C. 1.565





27


embedded image


—CN
—F
—H
—Cl
X107
—H
24.9° C. 1.5692





28


embedded image


—CN
—F
—H
—Cl
X108
—H
22.2° C. 1.5353





29


embedded image


—CN
—F
—H
—Cl
X109
—H
22.9° C. 1.5233





30


embedded image


—CN
—F
—H
—Cl
X110
—H
25.1° C. 1.5678





31


embedded image


—CN
—F
—H
—Cl
X111
—H
23.3° C. 1.5686





32


embedded image


—CN
—F
—H
—Cl
X112
—H
87-89





33


embedded image


—CN
—F
—H
—Cl
X113
—H
109-110





34


embedded image


—CN
—F
—H
—Cl
X114
—H
24.3° C. 1.5369





35


embedded image


—CN
—F
—H
—Cl
X115
—H
142-145





36


embedded image


—CN
—F
—H
—Cl
X116
—H
132-135





37


embedded image


—CN
—F
—H
—Cl
X117
—H
150-152





38


embedded image


—CN
—F
—H
—Cl
X118
—H
147-150





39


embedded image


—CN
—F
—H
—Cl
X119
—H
168-170





40


embedded image


—CN
—F
—H
—Cl
X120
—H
AMORPHOUS





41


embedded image


—CN
—F
—H
—Cl
X121
—H
173-174





42


embedded image


—CN
—F
—H
—Cl
X122
—H
22.2° C. 1.5402





43


embedded image


—CN
—F
—H
—Cl
X123
—H
103-105





44


embedded image


—CN
—F
—H
—Cl
X124
—H
23.1° C. 1.5426





45


embedded image


—CN
—F
—H
—Cl
X125
—H
108-112





46


embedded image


—CN
—F
—H
—Cl
X127
—H
AMORPHOUS





47


embedded image


—CN
—F
—H
—Cl
X128
—H
22° C. 1.5528





48


embedded image


—CN
—F
—H
—Cl
X129
—H
164-166





49


embedded image


—CN
—F
—H
—Cl
X130
—H
22.4° C. 1.5641





50


embedded image


—CN
—F
—H
—Cl
X130
—Cl
22.6° C. 1.5542





51


embedded image


—CN
—F
—H
—Cl
X131
—H
90-92





52


embedded image


—CN
—F
—H
—Cl
X132
—H
99-100





53


embedded image


—CN
—F
—H
—Cl
X133
—H
22.3° C. 1.5599





54


embedded image


—CN
—F
—H
—Cl
X134
—H
101-103





55


embedded image


—CN
—F
—H
—Cl
X135
—H
22.9° C. 1.5492





56


embedded image


—CN
—F
—H
—Cl
X136
—H
22.4° C. 1.5318





57


embedded image


—CN
—F
—H
—Cl
X137
—H
AMORPHOUS





58


embedded image


—CN
—F
—H
—Cl
X138
—H
22.5° C. 1.5478





59


embedded image


—CN
—F
—H
—Cl
X139
—H
22.5° C. 1.5187





60


embedded image


—CN
—F
—H
—Cl
X140
—H
140-143





61


embedded image


—CN
—F
—H
—Cl
X141
—H
123-126





62


embedded image


—CN
—F
—H
—Cl
X142
—H
22.3° C. 1.5768





63


embedded image


—CN
—F
—H
—Cl
X143
—H
21.9° C. 1.576





64


embedded image


—CN
—F
—H
—Cl
X144
—H
22° C. 1.5936





65


embedded image


—CN
—F
—H
—Cl
X145
—H
22.8° C. 1.586





66


embedded image


—CN
—F
—H
—Cl
X146
—H
22.6° C. 1.5772





67


embedded image


—CN
—F
—H
—Cl
X201
—H
22.5° C. 1.5598





68


embedded image


—CN
—F
—H
—Cl
X202
—H
22° C. 1.5388





69


embedded image


—CN
—F
—H
—Cl
X203
—H
154-159





70


embedded image


—CN
—F
—H
—Cl
X204
—H
23.2° C. 1.5358





71


embedded image


—CN
—F
—H
—Cl
X205
—H
VISCOUS OIL





72


embedded image


—CN
—F
—H
—Cl
X206
—H
AMORPHOUS





73


embedded image


—CN
—F
—H
—Cl
X207
—H
92-94





74


embedded image


—CN
—F
—H
—Cl
X208
—H
46-48





75


embedded image


—CN
—F
—H
—Cl
X209
—H
20.4° C. 1.53





76


embedded image


—CN
—F
—H
—Cl
X210
—H
22.2° C. 1.5414





77


embedded image


—CN
—F
—H
—Cl
X211
—H
104-106





78


embedded image


—CN
—F
—H
—Cl
X212
—H
VISCOUS OIL





79


embedded image


—CN
—F
—H
—Cl
X213
—H
22.8° C. 1.5467





80


embedded image


—CN
—F
—H
—Cl
X214
—H
VISCOUS OIL





81


embedded image


—CN
—F
—H
—Cl
X215
—H
24.9° C. 1.5454





82


embedded image


—CN
—F
—H
—Cl
X216
—H
22.5° C. 1.5379





83


embedded image


—CN
—F
—H
—Cl
X217
—H
117-119





84


embedded image


—CN
—F
—H
—Cl
X218
—H
25.5° C. 1.5389





85


embedded image


—CN
—F
—H
—Cl
X219
—H
23.3° C. 1.5526





86


embedded image


—CN
—F
—H
—Cl
X220
—H
VISCOUS OIL





87


embedded image


—CN
—F
—H
—Cl
X221
—H
22.4° C. 1.5349





88


embedded image


—CN
—F
—H
—Cl
X222
—H
AMORPHOUS





89


embedded image


—CN
—F
—H
—Cl
X223
—H
AMORPHOUS





90


embedded image


—CN
—F
—H
—Cl
X224
—H
VISCOUS OIL





91


embedded image


—CN
—F
—H
—Cl
X225
—H
133-136





92


embedded image


—CN
—F
—H
—Cl
X226
—H
VISCOUS OIL





93


embedded image


—CN
—F
—H
—Cl
X227
—H
23.7° C. 1.5342





94


embedded image


—CN
—F
—H
—Cl
X228
—H
22.1° C. 1.5396





95


embedded image


—CN
—F
—H
—Cl
X229
—H
22.5° C. 1.555





96


embedded image


—CN
—F
—H
—Cl
X230
—H
22.3° C. 1.5423





97


embedded image


—CN
—F
—H
—Cl
X231
—H
VISCOUS OIL





98


embedded image


—CN
—F
—H
—Cl
X232
—H
126-128





99


embedded image


—CN
—F
—H
—Cl
X233
—H
187-190





100


embedded image


—CN
—F
—H
—Cl
X234
—H
22.8° C. 1.5649





101


embedded image


—CN
—F
—H
—Cl
X235
—H
118-119





102


embedded image


—CN
—F
—H
—Cl
X236
—H
22.2° C. 1.5543





103


embedded image


—CN
—F
—H
—Cl
X237
—H
22.5° C. 1.5618





104


embedded image


—CN
—F
—H
—Cl
X238
—H
158-161





105


embedded image


—CN
—F
—H
—Cl
X239
—H
111-112





106


embedded image


—CN
—F
—H
—Cl
X240
—H
22.9° C. 1.5615





107


embedded image


—CN
—F
—H
—Cl
X241
—H
23.3° C. 1.5491





108


embedded image


—CN
—F
—H
—Cl
X242
—H
57-59





109


embedded image


—CN
—F
—H
—Cl
X243
—H
AMORPHOUS





110


embedded image


—CN
—F
—H
—Cl
X244
—H
AMORPHOUS





111


embedded image


—CN
—F
—H
—Cl
X245
—H
22.4° C. 1.5555





112


embedded image


—CN
—F
—H
—Cl
X246
—H
163-167





113


embedded image


—CN
—F
—H
—Cl
X247
—H
25.1° C. 1.5818





114


embedded image


—CN
—F
—H
—Cl
X248
—H
21.9° C. 1.5211





115


embedded image


—CN
—F
—H
—Cl
X249
—H
AMORPHOUS





116


embedded image


—CN
—F
—H
—Cl
X250
—H
VISCOUS OIL





117


embedded image


—CN
—F
—H
—Cl
X251
—H
AMORPHOUS





118


embedded image


—CN
—F
—H
—Cl
X252
—H
AMORPHOUS





119


embedded image


—CN
—F
—H
—Cl
X253
—H
23.6° C. 1.5483





120


embedded image


—CN
—F
—H
—Cl
X254
—H
24.4° C. 1.5548





121


embedded image


—CN
—F
—H
—Cl
X255
—H
24.3° C. 1.5535





122


embedded image


—CN
—F
—H
—Cl
X256
—H
AMORPHOUS





123


embedded image


—CN
—F
—H
—Cl
X257
—H
22.8° C. 1.5352





124


embedded image


—CN
—F
—H
—Cl
X258
—H
22.2° C. 1.545





125


embedded image


—CN
—F
—H
—Cl
X259
—H
25.1° C. 1.5606





126


embedded image


—CN
—F
—H
—Cl
X260
—H
24.8° C. 1.539





127


embedded image


—CN
—F
—H
—Cl
X261
—H
24.5° C. 1.5428





128


embedded image


—CN
—F
—H
—Cl
X301
—H
23.8° C. 1.5161





129


embedded image


—CN
—F
—H
—Cl
X302
—H
24.6° C. 1.5261





130


embedded image


—CN
—F
—H
—Cl
—F
—H
22.7° C. 1.5733





131


embedded image


—CN
—F
—H
—Cl
—NH2
—H
83-85





132


embedded image


—CN
—F
—H
—Cl
—NO2
—H
20.3° C. 1.5982





133


embedded image


—CN
—F
—H
—Cl
N002
—H
116-118





134


embedded image


—CN
—F
—H
—Cl
N003
—H
135-137





135


embedded image


—CN
—F
—H
—Cl
N004
—H
134-137





136


embedded image


—CN
—F
—H
—Cl
N006
—H
22.4° C. 1.5425





137


embedded image


—CN
—F
—H
—Cl
—OH
—H
165-167





138


embedded image


—CN
—F
—H
—Cl
T045
—H
22.3° C. 1.5956





139


embedded image


—CN
—F
—H
—Cl
T001
—H
65-67





140


embedded image


—CN
—F
—H
—Cl
T002
—H
22.4° C. 1.5776





141


embedded image


—CN
—F
—H
—Cl
T003
—H
88-89





142


embedded image


—CN
—F
—H
—Cl
T003
—CH2CH═CH2
63-64





143


embedded image


—CN
—F
—H
—Cl
T003
—Cl
22.6° C. 1.5861





144


embedded image


—CN
—F
—H
—Cl
T003
—NO2
VISCOUS OIL





145


embedded image


—CN
—F
—H
—Cl
T005
—H
71-75





146


embedded image


—CN
—F
—H
—Cl
T006
—H
22.8° C. 1.5719





147


embedded image


—CN
—F
—H
—Cl
T007
—H
22.2° C. 1.56





148


embedded image


—CN
—F
—H
—Cl
T008
—H
75-78





149


embedded image


—CN
—F
—H
—Cl
T011
—H
110-113





150


embedded image


—CN
—F
—H
—Cl
T012
—H
55-58





151


embedded image


—CN
—F
—H
—Cl
T013
—H
22.4° C. 1.5745





152


embedded image


—CN
—F
—H
—Cl
T014
—H
22.2° C. 1.6089





153


embedded image


—CN
—F
—H
—Cl
T015
—H
110-113





154


embedded image


—CN
—F
—H
—Cl
T016
—H
156-158





155


embedded image


—CN
—F
—H
—Cl
T017
—H
151-153





156


embedded image


—CN
—F
—H
—Cl
S001
—H
61-64





157


embedded image


—CN
—F
—H
—Cl
S002
—H
22.4° C. 1.62





158


embedded image


—CN
—F
—H
—Cl
S003
—H
22.5° C. 1.6018





159


embedded image


—CN
—F
—H
—Cl
S004
—H
22.6° C. 1.5868





160


embedded image


—CN
—F
—H
—Cl
S005
—H
86-90





161


embedded image


—CN
—F
—H
—Cl
S006
—H
151-153





162


embedded image


—CN
—F
—H
—Cl
S007
—H
113-114





163


embedded image


—CN
—F
—H
—Cl
T010
—H
103-105





164


embedded image


—CN
—F
—H
—Cl
H002
—H
128-131

















165


embedded image


—CN
—F
—H
—Cl


embedded image


145-147





166


embedded image


—CN
—F
—H
—Cl


embedded image


99-100





167


embedded image


—CN
—F
—H
—Cl


embedded image


145-147





168


embedded image


—CN
—F
—H
—Cl


embedded image


VISCOUS OIL


















169


embedded image


—CN
—F
—H
—Br
X208
—H
20.2° C. 1.5553





170


embedded image


—CN
—F
—H
—Br
T003
—H
83-85

















171


embedded image


—CN
—F
—H


embedded image


—H
153-157





172


embedded image


—CN
—F
—H


embedded image


—H
231-234





173


embedded image


—CN
—F
—H


embedded image


—H
142-144





174


embedded image


—CN
—F
—H


embedded image


—Cl
130-132


















175


embedded image


—CN
—CH3
—H
—CH3
—H
—CH3
78-83





176


embedded image


—CN
—CH3
—H
—Br
—H
—H
58-60





177


embedded image


—CN
—CH3
—H
—Br
—H
—CH3
118-120





178


embedded image


—CN
—Cl
—H
—Cl
—H
—H
20.7° C. 1.6158





179


embedded image


—CN
—Cl
—H
—Cl
X101
—H
163-165





180


embedded image


—CN
—Cl
—H
—Cl
X112
—H
104-106





181


embedded image


—CN
—Cl
—H
—Cl
X126
—H
156-158





182


embedded image


—CN
—Cl
—H
—Cl
X136
—H
84-86





183


embedded image


—CN
—Cl
—H
—Cl
X208
—H
22° C. 1.551





184


embedded image


—CN
—Cl
—H
—Cl
T003
—H
VISCOUS OIL





185


embedded image


—CN
—Cl
—H
—Cl
T010
—H
79-81





186


embedded image


—CN
—Cl
—H
—Cl
—NO2
—H
101-104





187


embedded image


—CN
—Cl
—H
—Cl
N005
—H
AMORPHOUS





188


embedded image


—CN
H001
—H
—Cl
S006
—H
AMORPHOUS





189


embedded image


—CH═NOH
—F
—H
—Cl
—OC3H7
—H
150-154





190


embedded image


—CH═NOCH3
—F
—H
—Cl
T003
—H
73-75





191


embedded image


—CH═NOC2H5
—F
—H
—Cl
T003
—H
22.4° C. 1.5796





192


embedded image


—CH═NOCH2Ph
—F
—H
—Cl
—OH
—H
AMORPHOUS





193


embedded image


—CH═NOCH2Ph
—F
—H
—Cl
—OC3H7
—H
20.6° C. 1.5922





194


embedded image


—CH═NOCH2Ph
—F
—H
—Cl
T003
—H
58-62





195


embedded image


—CH═NOCH2Ph
—F
—H
—Cl
T004
—H
20.2° C. 1.609





196


embedded image


—CH═NOCH2CH═CH2
—F
—H
—Cl
T003
—H
22.6° C. 1.5852





197


embedded image


—CH═NOCH2CH═CHCl
—F
—H
—Cl
T003
—H
20.6° C. 1.5862





198


embedded image




embedded image


—F
—H
—Cl
T003
—H
186-188





199


embedded image




embedded image


—F
—H
—Cl
T003
—H
AMORPHOUS





200


embedded image




embedded image


—F
—H
—Cl
X208
—H
147-150





201


embedded image




embedded image


—F
—H
—Cl
X208
—H
AMORPHOUS





202


embedded image




embedded image


—F
—H
—Cl
X208
—H
20.5° C. 1.558





203


embedded image




embedded image


—F
—H
—Cl
T003
—H
20.5° C. 1.584





204


embedded image




embedded image


—F
—H
—Cl
X208
—H
AMORPHOUS





205


embedded image




embedded image


—F
—H
—Cl
T003
—H
AMORPHOUS





206


embedded image




embedded image


—F
—H
—Cl
T003
—H
143-146





207


embedded image




embedded image


—F
—H
—Cl
T003
—H
79-81





208


embedded image




embedded image


—F
—H
—Cl
T003
—H
AMORPHOUS





209


embedded image




embedded image


—F
—H
—Cl
T003
—H
AMORPHOUS





210


embedded image




embedded image


—F
—H
—Cl
T003
—H
AMORPHOUS





211


embedded image


—CN
—F
—H
—Cl
T003
—H
20.5° C. 1.5805





212


embedded image


—CN
—Cl
—H
—Cl
—H
—H
22° C. 1.5825





213


embedded image


—CN
—F
—H
—Cl
T003
—H
20.5° C. 1.5636





214


embedded image


—CN
—F
—H
—Cl
T003
—H
80-83





215


embedded image


—CN
—Cl
—H
—Cl
—H
—H
21.4° C. 1.5927





216


embedded image


—CN
—F
—H
—Cl
T003
—H
129-132





217


embedded image


—CN
—F
—H
—Cl
T003
—H
20.6° C. 1.5475





218


embedded image


—CN
—F
—H
—Cl
T003
—H
20.6° C. 1.5739





219


embedded image


—CN
—F
—H
—Cl
T003
—H
107-108





220


embedded image


—CN
—F
—H
—Cl
T003
—H
117-120





221


embedded image


—CN
—F
—H
—Cl
T003
—H
20.4° C. 1.5972





222


embedded image


—CN
—F
—H
—Cl
T003
—H
20.3° C. 1.5926





223


embedded image


—CN
—H
—H
—NO2
—H
—H
113-115





224


embedded image


—CN
—H
—H
—Cl
X102
—H
20.6° C. 1.5957





225


embedded image


—CN
—F
—H
—Cl
—H
—H
20.5° C. 1.5882





226


embedded image


—CN
—F
—H
—Cl
T003
—H
19.7° C. 1.5673





227


embedded image


—CN
—Cl
—H
—Cl
—H
—H
20.6° C. 1.6045





228


embedded image


—CN
—F
—H
—Cl
T003
—H
20° C. 1.5545





229


embedded image


—CN
—F
—H
—Cl
T003
—H
21.2° C. 1.5542





230


embedded image


—CN
—F
—H
—Cl
T003
—H
19.5° C. 1.556





231


embedded image


—CN
—Cl
—H
—Cl
—H
—H
149-151





232


embedded image


—CN
—H
—H
—CN
X112
—H
100-102





233


embedded image


—CN
—H
—H
—CN
X226
—H
23° C. 1.5497





234


embedded image


—CN
—H
—H
T045
—H
—H
68-70





235


embedded image


—CN
—H
—H
—OPh
—H
—H
114-117





236


embedded image


—CN
—H
—Cl
—Cl
—Cl
—H
110-112





237


embedded image


—CN
—F
—H
—Cl
X101
—H
190-193





238


embedded image


—CN
—F
—H
—Cl
X112
—H
68-71





239


embedded image


—CN
—F
—H
—Cl
X206
—H
22.7° C. 1.5421





240


embedded image


—CN
—F
—H
—Cl
X208
—H
22.4° C. 1.5385





241


embedded image


—CN
—F
—H
—Cl
X217
—H
22.9° C. 1.5449





242


embedded image


—CN
—F
—H
—Cl
X226
—H
23.3° C. 1.5585





243


embedded image


—CN
—F
—H
—Cl
T003
—H
114-117





244


embedded image


—CN
—Cl
—H
—Cl
—H
—H
121-122





245


embedded image


—CH═NOCH2CH═CHCl
—F
—H
—Cl
T003
—H
20.5° C. 1.5809





246


embedded image




embedded image


—Cl
—H
—Cl
—H
—H
235-236.5





247


embedded image


—CN
—Cl
—H
—Cl
—H
—H
22.2° C. 1.637





248


embedded image


—CN
—Cl
—H
—Cl
—H
—H
130-134





249


embedded image


—CN
—F
—H
—Cl
T003
—H
19.8° C. 1.5853





250


embedded image


—CN
—F
—H
—Cl
T003
—H
20.6° C. 1.5372





251


embedded image


—CN
—F
—H
—Cl
T003
—H
20.6° C. 1.5311





252


embedded image


—CN
—F
—H
—Cl
H003
—H
AMORPHOUS

















253


embedded image


—CN
—F
—H
—Cl


embedded image


212-214





254


embedded image


—CN
—F
—H
—Cl


embedded image


194-195





255


embedded image


—CN
—F
—H
—Cl


embedded image


147-149





256


embedded image


—CN
—F
—H
—Cl


embedded image


204-205


















257


embedded image


—CN
T008
—H
—Cl
X112
—H
112-113





258


embedded image


—CN
—F
—H
—Cl
X214
—H
AMORPHOUS





259


embedded image


—CN
—F
—H
—Cl
X211
—H
20.6° C. 1.4914





260


embedded image


—CN
—F
—H
—Cl
X148
—H
167-170

















261


embedded image


—CN
—F
—H
—Cl


embedded image


22° C. 1.564


















262


embedded image


—CN
—F
—H
—Cl
T003
—H
127-129





263


embedded image


—CN
—F
—H
—Cl
X130
—H
20.6° C. 1.5077





264


embedded image


—CN
—F
—H
—Cl
X214
—H
VISCOUS OIL





265


embedded image


—CN
—F
—H
—Cl
X147
—H
123-126





266


embedded image


—CN
—F
—H
—Cl
X147
—H
91-92





267


embedded image


—CN
—F
—H
—Cl
T003
—H
VISCOUS OIL





268


embedded image


—CN
—F
—H
—Cl
T003
—H
VISCOUS OIL





269


embedded image


—CN
—F
—H
—Cl


embedded image


—H
22° C. 1.5689





270


embedded image


—CN
—F
—H
—Cl
X201
—H
22° C. 1.52





271


embedded image


—CN
—F
—H
—Cl
T003
—H
20.6° C. 1.5958





272


embedded image


—CN
—Cl
—H
—Cl
—H
—H
79-81





273


embedded image


—CN
—F
—H
—Cl
T045
—H
142-144

















274


embedded image


—CN
—F
—H


embedded image


—H
147-149


















275


embedded image


—CN
—F
—H
—Cl
—H
—H
20.6° C. 1.526





276


embedded image


—CN
—F
—H
—Cl
—NO2
—H
115-117





277


embedded image


—CN
—F
—H
—Cl
—NH2
—H
99-102





278


embedded image


—CN
—F
—H
—Cl
S008
—H
67-70





279


embedded image


—CN
—F
—H
—Cl
S008
—H
20.4° C. 1.6283





280


embedded image


—CN
—F
—H
—Cl
—OH
—H
92-95





281


embedded image


—CN
—F
—H
—Cl
T006
—H
20.5° C. 1.522





282


embedded image


—CN
—F
—H
—Cl
T008
—H
72-74





283


embedded image


—CN
—F
—H
—Cl
S009
—H
169-170





284


embedded image


—CN
—F
—H
—Cl
X148
—H
AMORPHOUS





285


embedded image


—CN
—F
—H
—Cl
H004
—H
AMORPHOUS





286


embedded image


—CN
—F
—H
—Cl
N003
—H
181-184





287


embedded image


—CN
—F
—H
—Cl
T018
—H
73-75





288


embedded image


—CN
—F
—H
—Cl
T019
—H
84-87





289


embedded image


—CN
—F
—H
—Cl
H005
—H
102-105





290


embedded image


—CN
—F
—H
—Cl
N007
—H
150-155





291


embedded image


—CN
—F
—H
—Cl
H006
—H
118-120





292


embedded image


—CN
—F
—H
—Cl
H007
—H
AMORPHOUS





293


embedded image




embedded image


—Cl
—H
—Cl
X136
—H
160-163





294


embedded image




embedded image


—Cl
—H
—Cl
T010
—H
173-175





295


embedded image


—CN
—F
—H
—Cl
T020
—H
50-53





296


embedded image


—CN
—Cl
—H
—Cl
—H
—H
VISCOUS OIL





297


embedded image


—CN
—F
—H
—Cl
T002
—H
92-95





298


embedded image


—CN
—F
—H
—Cl
T021
—H
88-90





299


embedded image


—CN
—F
—H
—Cl
T003
—H
20.5° C. 1.5845





300


embedded image


—CN
—F
—H
—Cl
X125
—H
126-128





301


embedded image


—CN
—F
—H
—Cl
T022
—H
93-95





302


embedded image


—CN
—F
—H
—Cl
N001
—H
VISCOUS OIL





303


embedded image


—CN
—F
—H
—Cl
X262
—H
AMORPHOUS





304


embedded image


—CN
—F
—H
—Cl
X263
—H
118-120





305


embedded image


—CN
—F
—H
—Cl
H008
—H
20.6° C. 1.5799





306


embedded image


—CN
—F
—H
—Cl
X264
—H
AMORPHOUS





307


embedded image


—CN
—F
—H
—Cl
H009
—H
20.4° C. 1.5698





308


embedded image


—CN
—F
—H
—Cl
T023
—H
96-98





309


embedded image


—CN
—F
—H
—Cl
T001
—H
79-81





310


embedded image


—CN
—F
—H
—Cl
T024
—H
58-59





311


embedded image


—CN
—F
—H
—Cl
H010
—H
AMORPHOUS





312


embedded image


—CN
—F
—H
—Cl
T025
—H
20.5° C. 1.5155





313


embedded image


—CN
—F
—H
—Cl
T026
—H
62-64





314


embedded image


—CN
—F
—H
—Cl
H011
—H
AMORPHOUS





315


embedded image


—CN
—F
—H
—Cl
C003
—H
143-145





316


embedded image


—CN
—F
—H
—Cl
H012
—H
77-79





317


embedded image


—CN
—F
—H
—Cl
T027
—H
69-71





318


embedded image


—CN
—F
—H
—Cl
H018
—H
AMORPHOUS





319


embedded image


—CN
—F
—H
—Cl
H013
—H
196-201





320


embedded image


—CN
—F
—H
—Cl
T003
—H
20.6° C. 1.5705





321


embedded image


—CN
—F
—H
—Cl
H014
—H
VISCOUS OIL





322


embedded image


—CN
—F
—H
—Cl
H015
—H
20.6° C. 1.5884





323


embedded image


—CN
—F
—H
—Cl
H016
—H
136-140





324


embedded image


—CN
—F
—H
—Cl
H017
—H
20.7° C. 1.5786





325


embedded image


—CN
—F
—H
—Cl
T003
—H
AMORPHOUS





326


embedded image


—CN
—F
—H
—Cl
T003
—H
109-112





327


embedded image


—CN
—F
—H
—Cl
T003
—H
VISCOUS OIL





328


embedded image


—CN
—H
—CF3
—H
—CF3
—H
20.7° C. 1.4608





329


embedded image


—CN
—F
—H
—Cl
X112
—H
94-96





330


embedded image


—CN
—F
—H
—Cl
X101
—H
155-159





331


embedded image


—CN
—F
—H
—Cl
X149
—H
112-116





332


embedded image


—CN
—F
—H
—Cl
C002
—H
21.3° C. 1.5840





333


embedded image


—CN
—F
—H
—Cl
X103
—H
93-96





334


embedded image


—CN
—F
—H
—Cl
X151
—H
AMORPHOUS





335


embedded image


—CN
—F
—H
—Cl
T003
—H
21.0° C. 1.5793





336


embedded image


—CN
—F
—H
—Cl
H005
—H
AMORPHOUS





337


embedded image


—CN
—F
—H
—Cl
H007
—H
AMORPHOUS

















338


embedded image


—CN
—F
—H


embedded image


—H
127-129


















339


embedded image


—CN
—F
—H
—Cl
T014
—H
AMORPHOUS





340


embedded image


—CN
—F
—H
—Cl
T028
—H
20.7° C. 1.5342





341


embedded image


—CN
—F
—H
—Cl
T029
—H
20.9° C. 1.5523





342


embedded image


—CN
—H
—H
—Cl
—OCH3
—H
136-139





343


embedded image


—CN
—H
—H
—CF3
—H
—H
94-96





344


embedded image


—CN
—F
—H
—Cl
T003
—H
94-96





345


embedded image


—CN
—F
—H
—Cl
T003
—H
95-97





346


embedded image


—CN
—F
—H
—Cl
T003
—H
20.7° C. 1.5569





347


embedded image


—CN
—F
—H
—Cl
T003
—H
121-124





348


embedded image


—CN
—F
—H
—Cl
T003
—H
22° C. 1.5920





349


embedded image


—CN
—F
—H
—Cl
T003
—H
22.8° C. 1.5783

















350


embedded image


—CN
—F
—H


embedded image


—H
102-105


















351


embedded image


—CN
—F
—H
—Cl
T003
—H
98-101





352


embedded image


—CN
—F
—H
—Cl
T021
—H
84-86





353


embedded image


—CN
—F
—H
—Cl
T030
—H
20.8° C. 1.5609





354


embedded image


—CN
—F
—H
—Cl
—OCH2C2F5
—H
62-65





355


embedded image


—CN
—F
—H
—Cl
X150
—H
17.1° C. 1.5221





356


embedded image


—CN
—F
—H
—Cl
X152
—H
22.5° C. 1.5235





357


embedded image


—CN
—F
—H
—Cl
X153
—H
71-74





358


embedded image


—CN
—H
—H
—H
T003
—H
23.4° C. 1.5208





359


embedded image


—CN
—F
—H
—Cl
T003
—H
20.5° C. 1.6050





360


embedded image


—CN
—F
—H
—Cl
T003
—H
20.5° C. 1.5700





361


embedded image


—CN
—F
—H
—Cl
X265
—H
20.7° C. 1.4995





362


embedded image


—CN
—F
—H
—Cl
X266
—H
86-88





363


embedded image


—CN
—F
—H
—Cl
X267
—H
20.5° C. 1.5228





364


embedded image


—CN
—F
—H
—Cl
X268
—H
106-108





365


embedded image


—CN
—F
—H
—Cl
T031
—H
20.6° C. 1.5035





366


embedded image


—CN
—F
—H
—Cl
T032
—H
111-113





367


embedded image


—CN
—F
—H
—Cl
T033
—H
20.7° C. 1.5452





368


embedded image


—CN
—F
—H
—Cl
T034
—H
82-85





369


embedded image


—CN
—F
—H
—Cl
T003
—H
21° C. 1.5268





370


embedded image


—CN
—F
—H
—Cl
T035
—H
101-103





371


embedded image


—CN
—F
—H
—Cl
T036
—H
20.6° C. 1.5510





372


embedded image


—CN
—F
—H
—Cl
T037
—H
20.5° C. 1.5128





373


embedded image


—CN
—F
—H
—Cl
T003
—H
20.2° C. 1.5418





374


embedded image


—CN
—F
—H
—Cl
T038
—H
89-91





375


embedded image


—CN
—F
—H
—Cl
T039
—H
77-80





376


embedded image


—CN
—F
—H
—Cl
T040
—H
20.5° C. 1.5383





377


embedded image


—CN
—F
—H
—Cl
T040
—H
20.4° C. 1.5913





378


embedded image


—CN
—F
—H
—Cl
T041
—H
20.4° C. 1.5353





379


embedded image


—CN
—F
—H
—Cl
T041
—H
20.4° C. 1.5874





380


embedded image


—CN
—F
—H
—Cl
T042
—H
144-148





381


embedded image


—CN
—F
—H
—Cl
C001
—H
20.4° C. 1.5587





382


embedded image


—CN
—F
—H
—Cl
—CHO
—H
85-88





383


embedded image


—CN
—F
—H
—Cl
T003
—H
166-168





384


embedded image


—CN
F
H
F
T003
H
20.5° C. 1.5528





385


embedded image


—CN
F
H
F
T043
H
20.7° C. 1.5192





386


embedded image


—CN
F
H
Cl


embedded image


H
130-132





387


embedded image


—CN
F
H
Br
T003
H
81-84





388


embedded image


—CN
F
H
Cl
X303
H
20.6° C. 1.5514





389


embedded image


—CN
F
H
Cl
T044
H
20.5° C. 1.5744





390


embedded image


—CN
F
H
Cl
T045


embedded image


156-158





391


embedded image


—CN
F
H
Cl
T045
—NH2
201-204





392


embedded image


—CN
F
H
Cl
X304
H
148-150





393


embedded image


—CN
F
H
Cl
X304
H
20.7° C. 1.5612





394


embedded image


—CN
F
H
Cl
T046
H
40-42





395


embedded image


—CN
F
H
Cl
T047
H
55-57





396


embedded image


—CN
F
H
Cl
T048
H
20.4° C. 1.5704





397


embedded image


—CN
F
H
Cl
T049
H
55-57





398


embedded image


—CN
F
H
Cl


embedded image


H
VISCOUS OIL





399


embedded image


—CN
F
H
Cl
T050
H
114-116





400


embedded image


—CN
F
H
Cl
T051
H
123-125





401


embedded image


—CN
F
H
Cl
T052
H
20.5° C. 1.5506





402


embedded image


—CN
F
H
Cl
T053
H
20.7° C. 1.5308





403


embedded image


—CN
F
H
Cl
T054
H
94-96





404


embedded image


—CN
F
H
Cl
X305
H
55-57





405


embedded image


—CN
F
H
Cl
T055
H
20.3° C. 1.5543





406


embedded image


—CN
F
H
Cl
X306
H
VISCOUS OIL





407


embedded image


—CN
F
H
Cl
X307
H
62-64





408


embedded image


—CN
F
H
Cl
X308
H
VISCOUS OIL





409


embedded image


—CN
F
H
Cl
X309
H
64-66





410


embedded image


—CN
F
H
Cl
X310
H
59-61





411


embedded image


—CN
F
H
Cl
T056
H
20.4° C. 1.5434





412


embedded image


—CN
F
H
Cl
T057
H
80-83





413


embedded image


—CN
F
H
Cl
T058
H
60-62





414


embedded image


—CN
F
H
Cl
T059
H
104-105





415


embedded image


—CN
F
H
Cl
T060
H
AMORPHOUS





416


embedded image


—CN
F
H
Cl
X311
H
113-115





417


embedded image


—CN
F
H
Cl
X312
H
AMORPHOUS





418


embedded image


—CN
F
H
Cl
X313
H
99-101





419


embedded image


—CN
F
H
Cl
T061
H
119-121





420


embedded image


—CN
F
H
Cl
T062
H
123-125





421


embedded image


—CN
F
H
Cl
T063
H
20.2° C. 1.5425





422


embedded image


—CN
F
H
Cl
T064
H
93-96





423


embedded image


—CN
F
H
Cl
X314
H
VISCOUS OIL





424


embedded image


—CN
F
H
Cl
X315
H
103-105





425


embedded image


—CN
F
H
Cl
X316
H
88-90





426


embedded image


—CN
F
H
Cl
T065
H
115-117

















427


embedded image


—CN
F
H


embedded image


H
20.5° C. 1.5338





428


embedded image


—CN
F
H


embedded image


H
115-117


















429


embedded image


—CN
F
H
Cl
T066
H
VISCOUS OIL





430


embedded image


—CN
F
H
Cl
T003
H
AMORPHOUS





431


embedded image


—CN
F
H
Cl
T003
H
20.4° C. 1.5502





432


embedded image


—CN
F
H
Cl
X317
H
VISCOUS OIL





433


embedded image


—CN
F
H
Cl
X318
H
79-81





434


embedded image


—CN
F
H
Cl
X319
H
VISCOUS OIL





435


embedded image


—CN
F
H
Cl
T067
H
94-97





436


embedded image


—CN
F
H
Cl
T003
H
VISCOUS OIL





437


embedded image


—CN
F
H
Cl
X320
H
VISCOUS OIL





438


embedded image


—CN
F
H
Cl
T068
H
109-111





439


embedded image


—CN
F
H
Cl
T069
H
50-52





440


embedded image


—CN
F
H
Cl
T070
H
VISCOUS OIL





441


embedded image


—CN
F
H
Cl
T070
H
99-100





442


embedded image


—CN
F
H
Cl
T071
H
VISCOUS OIL





443


embedded image


—CN
F
H
Cl
X321
H
VISCOUS OIL





444


embedded image


—CN
F
H
Cl
T072
H
102-104





445


embedded image


—CN
F
H
Cl
T073
H
19.9° C. 1.5564





446


embedded image


—CN
F
H


embedded image


F
H
20.5° C. 1.5142





447


embedded image


—CN
F
H
Cl
T074
H
62-65





448


embedded image


—CN
F
H
Cl
T075
H
66-69





449


embedded image


—CN
F
H
Cl
T076
H
97-99





450


embedded image


—CN
F
H
Cl
T077
H
20.9° C. 1.5753





451


embedded image


—CN
F
H
Cl
X322
H
AMORPHOUS





452


embedded image


—CN
F
H
Cl
T078
H
135-137





453


embedded image


—CN
F
H
Cl
T079
H
20.7° C. 1.4856





454


embedded image


—CN
F
H
Cl
T080
H
20.7° C. 1.5276





455


embedded image


—CN
F
H
Cl
X323
H
VISCOUS OIL





456


embedded image


—CN
F
H
Cl
X324
H
111-113





457


embedded image


—CN
F
H
CO2Et
N001
H






458


embedded image


—CH═NOH
Cl
H
SMe
N002
H






459


embedded image


—CH═NOCH2Ph
Br
H
Br
N003
H






460


embedded image




embedded image


NEt2
SPh
H
N007
H






461


embedded image




embedded image


OMe
H
H
S001
H






462


embedded image




embedded image


Bn
H
Cl
S002
H






463


embedded image




embedded image


SH
H
NEt2
S003
H






464


embedded image




embedded image


SMe
H
H
S004
H






465


embedded image




embedded image


Me
H
H
S005
H






466


embedded image




embedded image


CH═CH2
OCF3
H
S006
H






467


embedded image




embedded image




embedded image


Me
H
S007
H






468


embedded image




embedded image


Ac
NO2
H
S008
H






469


embedded image




embedded image


CO2Et
H
H
S009
H






470


embedded image




embedded image


COPh
H
H
H001
H






471


embedded image




embedded image


H
CN
H
H002
H






472


embedded image




embedded image


CONH2
H
H
H003
H






473


embedded image




embedded image


T001
CF3
H
Br
H






474


embedded image




embedded image


T002
OiPr
H
H
H


















475


embedded image




embedded image


T003
OCONH
H
H



















476


embedded image




embedded image


T004
Bn
H
H
H






477


embedded image




embedded image


T005
NEt2
H
H
H






478


embedded image




embedded image


T006
OH
H
H
H






479


embedded image




embedded image


T007
Br
H
H
H






480


embedded image




embedded image


T008
Cl
H
H
H






481


embedded image




embedded image


T009
F
H
H
H






482


embedded image




embedded image


Me
T010
F
H
CO2Et






483


embedded image




embedded image


F
T011
Cl
H
SMe






484


embedded image


—CN
Cl
T012
Br
H
Br






485


embedded image


—CH═NOH
Br
T013
CN
H
Me






486


embedded image


—CH═NOCH2Ph
CN
T014
NO2
H
Et






487


embedded image




embedded image


CF3
T018
Bn
H
Cl






488


embedded image




embedded image


CO2Me
T019
SH
H
NEt2






489


embedded image




embedded image


F
H004
SMe
H
H






490


embedded image




embedded image


Cl
H005
Me
H
H






491


embedded image




embedded image


H
H006
CH═CH2
OCF3
H






492


embedded image




embedded image


H
H007


embedded image


Me
H






493


embedded image




embedded image


H
X101
Ac
NO2
H






494


embedded image




embedded image


CO2Et
X102
CO2Et
H
H






495


embedded image




embedded image


Et
X103
COPh
H
H






496


embedded image




embedded image


iPr
X104
H
CN
H






497


embedded image




embedded image


Me
X105
CONH2
H
H






498


embedded image




embedded image


Bn
X106
Cl
Me
Bn






499


embedded image




embedded image


SH
X107
NEt2
F
NEt2






500


embedded image




embedded image


SMe
X108
H
Cl
OH






501


embedded image




embedded image


Me
X109
H
Br
Br






502


embedded image




embedded image


CH═CH2
X110
H
CN
Cl






503


embedded image




embedded image




embedded image


X111
H
H
F






504


embedded image




embedded image


Ac
X112
H
Me
SH






505


embedded image




embedded image


CO2Et
X113
H
F
SMe






506


embedded image




embedded image


COPh
X114
H
CF3
Me






507


embedded image




embedded image


H
X115
H
CO2Me
CH═CH2






508


embedded image




embedded image


CONH2
X116
H
F


embedded image








509


embedded image




embedded image


H
Ac
X117
Cl
H






510


embedded image




embedded image


H
CO2Et
X118
H
H






511


embedded image


—CN
Cl
COPh
X119
H
H






512


embedded image


—CH═NOH
NEt2
H
X120
H
H






513


embedded image


—CH═NOCH2Ph
H
CONH2
X121
CO2Et
H






514


embedded image




embedded image


H
H
X125
Me
Me






515


embedded image




embedded image


H
H
X126
F
F






516


embedded image




embedded image


H
H
X127
CF3
Cl






517


embedded image




embedded image


H
H
X128
CO2Me
Br






518


embedded image




embedded image


H
H
X129
F
CN






519


embedded image




embedded image


H
H
X130
Cl
H






520


embedded image




embedded image


H
H
X131
H
Me






521


embedded image




embedded image


H
H
X132
H
F






522


embedded image




embedded image


H
H
X133
H
CF3






523


embedded image




embedded image


H
H
X134
CO2Et
CO2Me






524


embedded image




embedded image


H
H
X135
Et
H






525


embedded image




embedded image


H
H
X136
iPr
H






526


embedded image




embedded image


H
H
X137
Me
H






527


embedded image




embedded image


H
H
X138
Me
H






528


embedded image




embedded image


H
H
X139
F
H






529


embedded image




embedded image


H
H
X140
CF3
H






530


embedded image




embedded image


H
H
X141
CO2Me
H






531


embedded image




embedded image


Br
F
X142
H
H






532


embedded image




embedded image


H
Cl
X143
H
H






533


embedded image




embedded image


H
Br
X144
H
H






534


embedded image




embedded image


H
CN
X145
H
H






535


embedded image




embedded image


H
NO2
X146
H
H






536


embedded image




embedded image


H
OH
X147
H
F






537


embedded image




embedded image


H
NEt2
X148
H
Cl






538


embedded image


—CN
H
OMe
H
X201
Br






539


embedded image


—CH═NOH
H
Bn
H
X202
CN






540


embedded image


—CH═NOCH2Ph
H
SH
H
X203
OH






541


embedded image




embedded image


H


embedded image


H
X207
SH






542


embedded image




embedded image


Me
Ac
H
X208
F






543


embedded image




embedded image


SPh
CO2Et
H
X209
Cl






544


embedded image




embedded image


H
COPh
H
X210
Br






545


embedded image




embedded image


H
H
Me
X211
CN






546


embedded image




embedded image


H
CONH2
H
X212
NO2






547


embedded image




embedded image


H
H
H
X213
OH






548


embedded image




embedded image


H
H
H
X214
NEt2






549


embedded image




embedded image


OCF3
H
H
X215
OMe






550


embedded image




embedded image


Me
H
H
X216
Bn






551


embedded image




embedded image


NO2
H
H
X217
SH






552


embedded image




embedded image


H
H
H
X218
SMe






553


embedded image




embedded image


H
H
H
X219
OMe






554


embedded image




embedded image


CN
H
H
X220
Bn






555


embedded image




embedded image


H
H
H
X221
SH






556


embedded image




embedded image


H
H
H
X222
SMe






557


embedded image




embedded image


H
H
H
X223
Me






558


embedded image




embedded image


OCF3
H
H
X224
CH═CH2






559


embedded image




embedded image


Me
H
H
X225


embedded image








560


embedded image




embedded image


NO2
H
H
X226
Ac






561


embedded image




embedded image


H
H
H
X227
CO2Et






562


embedded image




embedded image


H
H
H
X228
COPh






563


embedded image




embedded image


CN
H
H
X229
H






564


embedded image




embedded image


NO2
CONEt2
H
X230
H






565


embedded image


—CN
CONH2
F
H
CO2Et
X231






566


embedded image


—CH═NOH
H
Cl
H
SMe
X232






567


embedded image


—CH═NOCH2Ph
H
Br
H
Br
X233






568


embedded image




embedded image


H
NEt2
SPh
H
X237






569


embedded image




embedded image


H
OMe
H
H
X238






570


embedded image




embedded image


H
Bn
H
Cl
X239






571


embedded image




embedded image


H
SH
H
NEt2
X240






572


embedded image




embedded image


H
SMe
H
H
X241






573


embedded image




embedded image


H
Me
H
H
X242






574


embedded image




embedded image


H
CH═CH2
OCF3
H
X243






575


embedded image




embedded image


H


embedded image


Me
H
X244






576


embedded image




embedded image


H
Ac
NO2
H
X245






577


embedded image




embedded image


H
CO2Et
H
H
X246






578


embedded image




embedded image


H
COPh
H
H
X247






579


embedded image




embedded image


H
H
CN
H
X248






580


embedded image




embedded image


CONEt2
CONH2
H
H
X249






581


embedded image




embedded image


Me
H
CO2Et
H
X250






582


embedded image




embedded image


NO2
H
SMe
H
X251






583


embedded image




embedded image


H
H
Br
H
X252






584


embedded image




embedded image


H
H
Me
H
X253






585


embedded image




embedded image


CN
H
Et
H
X254






586


embedded image




embedded image


H
Me
Me
H
X255






587


embedded image




embedded image


CF3
SPh
H
H
X256









588


embedded image




embedded image


CN
H
H
Me
X257






589


embedded image




embedded image


NO2
H
Cl
H
X258






590


embedded image




embedded image


Br
H
NEt2
H
X259






591


embedded image




embedded image


CF3
H
H
H
X260






592


embedded image


—CN
X261
H
H
H
Cl






593


embedded image


—CH═NOH
X302
OCF3
H
H
CO2Et






594


embedded image


—CH═NOCH2Ph
F
H
CO2Et
N001
H






595


embedded image




embedded image


NO2
H
Et
N005
H






596


embedded image




embedded image


OH
Me
Me
N006
H






597


embedded image




embedded image


NEt2
SPh
H
N007
H






598


embedded image




embedded image


OMe
H
H
S001
H






599


embedded image




embedded image


Bn
H
Cl
S002
H






600


embedded image




embedded image


SH
H
NEt2
S003
H






601


embedded image




embedded image


SMe
H
H
S004
H






602


embedded image




embedded image


Me
H
H
S005
H






603


embedded image




embedded image


CH═CH2
OCF3
H
S006
H






604


embedded image




embedded image




embedded image


Me
H
S007
H






605


embedded image




embedded image


Ac
NO2
H
S008
H






606


embedded image




embedded image


CO2Et
H
H
S009
H






607


embedded image




embedded image


COPh
H
H
H001
H






608


embedded image




embedded image


H
CN
H
H002
H






609


embedded image




embedded image


CONH2
H
H
H003
H






610


embedded image




embedded image


T001
CF3
H
Br
H






611


embedded image




embedded image


T002
OiPr
H
H
H


















612


embedded image




embedded image


T003
OCONH
H
H



















613


embedded image




embedded image


T004
Bn
H
H
H






614


embedded image




embedded image


T005
NEt2
H
H
H






615


embedded image




embedded image


T006
OH
H
H
H






616


embedded image




embedded image


T007
Br
H
H
H






617


embedded image




embedded image


T008
Cl
H
H
H






618


embedded image




embedded image


T009
F
H
H
H






619


embedded image


—CN
Me
T010
F
H
CO2Et






620


embedded image


—CH═NOH
F
T011
Cl
H
SMe






621


embedded image


—CH═NOCH2Ph
Cl
T012
Br
H
Br






622


embedded image




embedded image


Me
T016
NEt2
SPh
H






623


embedded image




embedded image


F
T017
OMe
H
H






624


embedded image




embedded image


CF3
T018
Bn
H
Cl






625


embedded image




embedded image


CO2Me
T019
SH
H
NEt2






626


embedded image




embedded image


F
H004
SMe
H
H






627


embedded image




embedded image


Cl
H005
Me
H
H






628


embedded image




embedded image


H
H006
CH═CH2
OCF3
H






629


embedded image




embedded image


H
H007


embedded image


Me
H






630


embedded image




embedded image


H
X101
Ac
NO2
H






631


embedded image




embedded image


CO2Et
X102
CO2Et
H
H






632


embedded image




embedded image


Et
X103
COPh
H
H






633


embedded image




embedded image


iPr
X104
H
CN
H






634


embedded image




embedded image


Me
X105
CONH2
H
H






635


embedded image




embedded image


Bn
X106
Cl
Me
Bn






636


embedded image




embedded image


SH
X107
NEt2
F
NEt2






637


embedded image




embedded image


SMe
X108
H
Cl
OH






638


embedded image




embedded image


Me
X109
H
Br
Br






639


embedded image




embedded image


CH═CH2
X110
H
CN
Cl






640


embedded image




embedded image




embedded image


X111
H
H
F






641


embedded image




embedded image


Ac
X112
H
Me
SH






642


embedded image




embedded image


CO2Et
X113
H
F
SMe






643


embedded image




embedded image


COPh
X114
H
CF3
Me






644


embedded image




embedded image


H
X115
H
CO2Me
CH═CH2






645


embedded image




embedded image


CONH2
X116
H
F


embedded image








646


embedded image


—CN
H
Ac
X117
Cl
H






647


embedded image


—CH═NOH
H
CO2Et
X118
H
H






648


embedded image


—CH═NOCH2Ph
Cl
COPh
X119
H
H






649


embedded image




embedded image


H
H
X123
iPr
H






650


embedded image




embedded image


H
H
X124
Me
H






651


embedded image




embedded image


H
H
X125
Me
Me






652


embedded image




embedded image


H
H
X126
F
F






653


embedded image




embedded image


H
H
X127
CF3
Cl






654


embedded image




embedded image


H
H
X128
CO2Me
Br






655


embedded image




embedded image


H
H
X129
F
CN






656


embedded image




embedded image


H
H
X130
Cl
H






657


embedded image




embedded image


H
H
X131
H
Me






658


embedded image




embedded image


H
H
X132
H
F






659


embedded image




embedded image


H
H
X133
H
CF3






660


embedded image




embedded image


H
H
X134
CO2Et
CO2Me






661


embedded image




embedded image


H
H
X135
Et
H






662


embedded image




embedded image


H
H
X136
iPr
H






663


embedded image




embedded image


H
H
X137
Me
H






664


embedded image




embedded image


H
H
X138
Me
H






665


embedded image




embedded image


H
H
X139
F
H






666


embedded image




embedded image


H
H
X140
CF3
H






667


embedded image




embedded image


H
H
X141
CO2Me
H






668


embedded image




embedded image


Br
F
X142
H
H






669


embedded image




embedded image


H
Cl
X143
H
H






670


embedded image




embedded image


H
Br
X144
H
H






671


embedded image




embedded image


H
CN
X145
H
H






672


embedded image




embedded image


H
NO2
X146
H
H






673


embedded image


—CN
H
OH
X147
H
F






674


embedded image


—CH═NOH
H
NEt2
X148
H
Cl






675


embedded image


—CH═NOCH2Ph
H
OMe
H
X201
Br






676


embedded image




embedded image


H
Me
H
X205
OMe






677


embedded image




embedded image


H
CH═CH
H
X206
Bn






678


embedded image




embedded image


H


embedded image


H
X207
SH






679


embedded image




embedded image


Me
Ac
H
X208
F






680


embedded image




embedded image


SPh
CO2Et
H
X209
Cl






681


embedded image




embedded image


H
COPh
H
X210
Br






682


embedded image




embedded image


H
H
Me
X211
CN






683


embedded image




embedded image


H
CONH2
H
X212
NO2






684


embedded image




embedded image


H
H
H
X213
OH






685


embedded image




embedded image


H
H
H
X214
NEt2






686


embedded image




embedded image


OCF3
H
H
X215
OMe






687


embedded image




embedded image


Me
H
H
X216
Bn






688


embedded image




embedded image


NO2
H
H
X217
SH






689


embedded image




embedded image


H
H
H
X218
SMe






690


embedded image




embedded image


H
H
H
X219
OMe






691


embedded image




embedded image


CN
H
H
X220
Bn






692


embedded image




embedded image


H
H
H
X221
SH






693


embedded image




embedded image


H
H
H
X222
SMe






694


embedded image




embedded image


H
H
H
X223
Me






695


embedded image




embedded image


OCF3
H
H
X224
CH═CH2






696


embedded image




embedded image


Me
H
H
X225


embedded image








697


embedded image




embedded image


NO2
H
H
X226
Ac






698


embedded image




embedded image


H
H
H
X227
CO2Et






699


embedded image




embedded image


H
H
H
X228
COPh






700


embedded image


—CN
CN
H
H
X229
H






701


embedded image


—CH═NOH
NO2
CONEt2
H
X230
H






702


embedded image


—CH═NOCH2Ph
CONH2
F
H
CO2Et
X231






703


embedded image




embedded image


H
NO2
H
Et
X235






704


embedded image




embedded image


H
OH
Me
Me
X236






705


embedded image




embedded image


H
NEt2
SPh
H
X237






706


embedded image




embedded image


H
OMe
H
H
X238






707


embedded image




embedded image


H
Bn
H
Cl
X239






708


embedded image




embedded image


H
SH
H
NEt2
X240






709


embedded image




embedded image


H
SMe
H
H
X241






710


embedded image




embedded image


H
Me
H
H
X242






711


embedded image




embedded image


H
CH═CH2
OCF3
H
X243






712


embedded image




embedded image


H


embedded image


Me
H
X244






713


embedded image




embedded image


H
Ac
NO2
H
X245






714


embedded image




embedded image


H
CO2Et
H
H
X246






715


embedded image




embedded image


H
COPh
H
H
X247






716


embedded image




embedded image


H
H
CN
H
X248






717


embedded image




embedded image


CONEt2
CONH2
H
H
X249






718


embedded image




embedded image


Me
H
CO2Et
H
X250






719


embedded image




embedded image


NO2
H
SMe
H
X251






720


embedded image




embedded image


H
H
Br
H
X252






721


embedded image




embedded image


H
H
Me
H
X253






722


embedded image




embedded image


CN
H
Et
H
X254






723


embedded image




embedded image


H
Me
Me
H
X255






724


embedded image




embedded image


CF3
SPh
H
H
X256






725


embedded image




embedded image


CN
H
H
Me
X257






726


embedded image




embedded image


NO2
H
Cl
H
X258






727


embedded image


—CN
Br
H
NEt2
H
X259






728


embedded image


—CH═NOH
CF3
H
H
H
X260






729


embedded image


—CH═NOCH2Ph
X261
H
H
H
Cl






730


embedded image




embedded image


Br
H
Br
N003
H






731


embedded image




embedded image


CN
H
Me
N004
H






732


embedded image




embedded image


NO2
H
Et
N005
H






733


embedded image




embedded image


OH
Me
Me
N006
H






734


embedded image




embedded image


NEt2
SPh
H
N007
H






735


embedded image




embedded image


OMe
H
H
S001
H






736


embedded image




embedded image


Bn
H
Cl
S002
H






737


embedded image




embedded image


SH
H
NEt2
S003
H






738


embedded image




embedded image


SMe
H
H
S004
H






739


embedded image




embedded image


Me
H
H
S005
H






740


embedded image




embedded image


CH═CH2
OCF3
H
S006
H






741


embedded image




embedded image




embedded image


Me
H
S007
H






742


embedded image




embedded image


Ac
NO2
H
S008
H






743


embedded image




embedded image


CO2Et
H
H
S009
H






744


embedded image




embedded image


COPh
H
H
H001
H






745


embedded image




embedded image


H
CN
H
H002
H






746


embedded image




embedded image


CONH2
H
H
H003
H






747


embedded image




embedded image


T001
CF3
H
Br
H






748


embedded image




embedded image


T002
OiPr
H
H
H


















749


embedded image




embedded image


T003
OCONH
H
H



















750


embedded image




embedded image


T004
Bn
H
H
H






751


embedded image




embedded image


T005
NEt2
H
H
H






752


embedded image




embedded image


T006
OH
H
H
H






753


embedded image




embedded image


T007
Br
H
H
H






754


embedded image


—CN
T008
Cl
H
H
H






755


embedded image


—CH═NOH
T009
F
H
H
H






756


embedded image


—CH═NOCH2Ph
Me
T010
F
H
CO2Et






757


embedded image




embedded image


CN
T014
NO2
H
Et






758


embedded image




embedded image


H
T015
OH
Me
Me






759


embedded image




embedded image


Me
T016
NEt2
SPh
H






760


embedded image




embedded image


F
T017
OMe
H
H






761


embedded image




embedded image


CF3
T018
Bn
H
Cl






762


embedded image




embedded image


CO2Me
T019
SH
H
NEt2






763


embedded image




embedded image


F
H004
SMe
H
H






764


embedded image




embedded image


Cl
H005
Me
H
H






765


embedded image




embedded image


H
H006
CH═CH2
OCF3
H






766


embedded image




embedded image


H
H007


embedded image


Me
H






767


embedded image




embedded image


H
X101
Ac
NO2
H






768


embedded image




embedded image


CO2Et
X102
CO2Et
H
H






769


embedded image




embedded image


Et
X103
COPh
H
H






770


embedded image




embedded image


iPr
X104
H
CN
H






771


embedded image




embedded image


Me
X105
CONH2
H
H






772


embedded image




embedded image


Bn
X106
Cl
Me
Bn






773


embedded image




embedded image


SH
X107
NEt2
F
NEt2






774


embedded image




embedded image


SMe
X108
H
Cl
OH






775


embedded image




embedded image


Me
X109
H
Br
Br






776


embedded image




embedded image


CH═CH2
X110
H
CN
Cl






777


embedded image




embedded image




embedded image


X111
H
H
F






778


embedded image




embedded image


Ac
X112
H
Me
SH






779


embedded image




embedded image


CO2Et
X113
H
F
SMe






780


embedded image




embedded image


COPh
X114
H
CF3
Me






781


embedded image


—CN
H
X115
H
CO2Me
CH═CH2






782


embedded image


—CH═NOH
CONH2
X116
H
F


embedded image








783


embedded image


—CH═NOCH2Ph
H
Ac
X117
Cl
H






784


embedded image




embedded image


H
CONH2
X121
CO2Et
H






785


embedded image




embedded image


H
H
X122
Et
H






786


embedded image




embedded image


H
H
X123
iPr
H






787


embedded image




embedded image


H
H
X124
Me
H






788


embedded image




embedded image


H
H
X125
Me
Me






789


embedded image




embedded image


H
H
X126
F
F






790


embedded image




embedded image


H
H
X127
CF3
Cl






791


embedded image




embedded image


H
H
X128
CO2Me
Br






792


embedded image




embedded image


H
H
X129
F
CN






793


embedded image




embedded image


H
H
X130
Cl
H






794


embedded image




embedded image


H
H
X131
H
Me






795


embedded image




embedded image


H
H
X132
H
F






796


embedded image




embedded image


H
H
X133
H
CF3






797


embedded image




embedded image


H
H
X134
CO2Et
CO2Me






798


embedded image




embedded image


H
H
X135
Et
H






799


embedded image




embedded image


H
H
X136
iPr
H






800


embedded image




embedded image


H
H
X137
Me
H






801


embedded image




embedded image


H
H
X138
Me
H






802


embedded image




embedded image


H
H
X139
F
H






803


embedded image




embedded image


H
H
X140
CF3
H






804


embedded image




embedded image


H
H
X141
CO2Me
H






805


embedded image




embedded image


Br
F
X142
H
H






806


embedded image




embedded image


H
Cl
X143
H
H






807


embedded image




embedded image


H
Br
X144
H
H






808


embedded image


—CN
H
CN
X145
H
H






809


embedded image


—CH═NOH
H
NO2
X146
H
H






810


embedded image


—CH═NOCH2Ph
H
OH
X147
H
F






811


embedded image




embedded image


H
SH
H
X203
OH






812


embedded image




embedded image


H
SMe
H
X204
NEt2






813


embedded image




embedded image


H
Me
H
X205
OMe






814


embedded image




embedded image


H
CH═CH2
H
X206
Bn






815


embedded image




embedded image


H


embedded image


H
X207
SH






816


embedded image




embedded image


Me
Ac
H
X208
F






817


embedded image




embedded image


SPh
CO2Et
H
X209
Cl






818


embedded image




embedded image


H
COPh
H
X210
Br






819


embedded image




embedded image


H
H
Me
X211
CN






820


embedded image




embedded image


H
CONH2
H
X212
NO2






821


embedded image




embedded image


H
H
H
X213
OH






822


embedded image




embedded image


H
H
H
X214
NEt2






823


embedded image




embedded image


OCF3
H
H
X215
OMe






824


embedded image




embedded image


Me
H
H
X216
Bn






825


embedded image




embedded image


NO2
H
H
X217
SH






826


embedded image




embedded image


H
H
H
X218
SMe






827


embedded image




embedded image


H
H
H
X219
OMe






828


embedded image




embedded image


CN
H
H
X220
Bn






829


embedded image




embedded image


H
H
H
X221
SH






830


embedded image




embedded image


H
H
H
X222
SMe






831


embedded image




embedded image


H
H
H
X223
Me






832


embedded image




embedded image


OCF3
H
H
X224
CH═CH2






833


embedded image




embedded image


Me
H
H
X225


embedded image








834


embedded image




embedded image


NO2
H
H
X226
Ac






835


embedded image


—CN
H
H
H
X227
CO2Et






836


embedded image


—CH═NOH
H
H
H
X228
COPh






837


embedded image


—CH═NOCH2Ph
CN
H
H
X229
H






838


embedded image




embedded image


H
Br
H
Br
X233






839


embedded image




embedded image


H
CN
H
Me
X234






840


embedded image




embedded image


H
NO2
H
Et
X235






841


embedded image




embedded image


H
OH
H
Me
X236






842


embedded image




embedded image


H
NEt2
SPh
H
X237






843


embedded image




embedded image


H
OMe
H
H
X238






844


embedded image




embedded image


H
Bn
H
Cl
X239






845


embedded image




embedded image


H
SH
H
NEt2
X240






846


embedded image




embedded image


H
SMe
H
H
X241






847


embedded image




embedded image


H
Me
H
H
X242






848


embedded image




embedded image


H
CH═CH2
OCF3
H
X243






849


embedded image




embedded image


H


embedded image


Me
H
X244






850


embedded image




embedded image


H
Ac
NO2
H
X245






851


embedded image




embedded image


H
CO2Et
H
H
X246






852


embedded image




embedded image


H
COPh
H
H
X247






853


embedded image




embedded image


H
H
CN
H
X248






854


embedded image




embedded image


CONEt2
CONH2
H
H
X249






855


embedded image




embedded image


Me
H
CO2Et
H
X250






856


embedded image




embedded image


NO2
H
SMe
H
X251






857


embedded image




embedded image


H
H
Br
H
X252






858


embedded image




embedded image


H
H
Me
H
X253






859


embedded image




embedded image


CN
H
Et
H
X254






860


embedded image




embedded image


H
Me
Me
H
X255






861


embedded image




embedded image


CF3
SPh
H
H
X256






862


embedded image


—CN
CN
H
H
Me
X257






863


embedded image


—CH═NOH
NO2
H
Cl
H
X258






864


embedded image


—CH═NOCH2Ph
Br
H
NEt2
H
X259






865


embedded image




embedded image


F
H
CO2Et
N001
H






866


embedded image




embedded image


Cl
H
SMe
N002
H






867


embedded image




embedded image


Br
H
Br
N003
H






868


embedded image




embedded image


CN
H
Me
N004
H






869


embedded image




embedded image


NO2
H
Et
N005
H






870


embedded image




embedded image


OH
Me
Me
N006
H






871


embedded image




embedded image


NEt2
SPh
H
N007
H






872


embedded image




embedded image


OMe
H
H
S001
H






873


embedded image




embedded image


Bn
H
Cl
S002
H






874


embedded image




embedded image


SH
H
NEt2
S003
H






875


embedded image




embedded image


SMe
H
H
S004
H






876


embedded image




embedded image


Me
H
H
S005
H






877


embedded image




embedded image


CH═CH2
OCF3
H
S006
H






878


embedded image




embedded image




embedded image


Me
H
S007
H






879


embedded image




embedded image


Ac
NO2
H
S008
H






880


embedded image




embedded image


CO2Et
H
H
S009
H






881


embedded image




embedded image


COPh
H
H
H001
H






882


embedded image




embedded image


H
CN
H
H002
H






883


embedded image




embedded image


CONH2
H
H
H003
H






884


embedded image




embedded image


T001
CF3
H
Br
H






885


embedded image




embedded image


T002
OiPr
H
H
H


















886


embedded image




embedded image


T003
OCONH
H
H



















887


embedded image




embedded image


T004
Bn
H
H
H






888


embedded image




embedded image


T005
NEt2
H
H
H






889


embedded image


—CN
T006
OH
H
H
H






890


embedded image


—CH═NOH
T007
Br
H
H
H






891


embedded image


—CH═NOCH2Ph
T008
Cl
H
H
H






892


embedded image




embedded image


Cl
T012
Br
H
Br






893


embedded image




embedded image


Br
T013
CN
H
Me






894


embedded image




embedded image


CN
T014
NO2
H
Et






895


embedded image




embedded image


H
T015
OH
Me
Me






896


embedded image




embedded image


Me
T016
NEt2
SPh
H






897


embedded image




embedded image


F
T017
OMe
H
H






898


embedded image




embedded image


CF3
T018
Bn
H
Cl






899


embedded image




embedded image


CO2Me
T019
SH
H
NEt2






900


embedded image




embedded image


F
H004
SMe
H
H






901


embedded image




embedded image


Cl
H005
Me
H
H






902


embedded image




embedded image


H
H006
CH═CH2
OCF3
H






903


embedded image




embedded image


H
H007


embedded image


ME
H






904


embedded image




embedded image


H
X101
Ac
NO2
H






905


embedded image




embedded image


CO2Et
X102
CO2Et
H
H






906


embedded image




embedded image


Et
X103
COPh
H
H






907


embedded image




embedded image


iPr
X104
H
CN
H






908


embedded image




embedded image


Me
X105
CONH2
H
H






909


embedded image




embedded image


Bn
X106
Cl
Me
Bn






910


embedded image




embedded image


SH
X107
NEt2
F
NEt2






911


embedded image




embedded image


SMe
X108
H
Cl
OH






912


embedded image




embedded image


Me
X109
H
Br
Br






913


embedded image




embedded image


CH═CH2
X110
H
CN
Cl






914


embedded image




embedded image




embedded image


X111
H
H
F






915


embedded image




embedded image


Ac
X112
H
Me
SH






916


embedded image


—CN
CO2Et
X113
H
F
SMe






917


embedded image


—CH═NOH
COPh
X114
H
CF3
Me






918


embedded image


—CH═NOCH2Ph
H
X115
H
CO2Me
CH═CH2






919


embedded image




embedded image


Cl
COPh
X119
H
H






920


embedded image




embedded image


NEt2
H
X120
H
H






921


embedded image




embedded image


H
CONH2
X121
CO2Et
H






922


embedded image




embedded image


H
H
X122
Et
H






923


embedded image




embedded image


H
H
X123
iPr
H






924


embedded image




embedded image


H
H
X124
Me
H






925


embedded image




embedded image


H
H
X125
Me
Me






926


embedded image




embedded image


H
H
X126
F
F






927


embedded image




embedded image


H
H
X127
CF3
Cl






928


embedded image




embedded image


H
H
X128
CO2Me
Br






929


embedded image




embedded image


H
H
X129
F
CN






930


embedded image




embedded image


H
H
X130
Cl
H






931


embedded image




embedded image


H
H
X131
H
Me






932


embedded image




embedded image


H
H
X132
H
F






933


embedded image




embedded image


H
H
X133
H
CF3






934


embedded image




embedded image


H
H
X134
CO2Et
CO2Me






935


embedded image




embedded image


H
H
X135
Et
H






936


embedded image




embedded image


H
H
X136
iPr
H






937


embedded image




embedded image


H
H
X137
Me
H






938


embedded image




embedded image


H
H
X138
Me
H






939


embedded image




embedded image


H
H
X139
F
H






940


embedded image




embedded image


H
H
X140
CF3
H






941


embedded image




embedded image


H
H
X141
CO2Me
H






942


embedded image




embedded image


Br
F
X142
H
H






943


embedded image


—CN
H
Cl
X143
H
H






944


embedded image


—CH═NOH
H
Br
X144
H
H






945


embedded image


—CH═NOCH2Ph
H
CN
X145
H
H






946


embedded image




embedded image


H
OMe
H
X201
Br






947


embedded image




embedded image


H
Bn
H
X202
CN






948


embedded image




embedded image


H
SH
H
X203
OH






949


embedded image




embedded image


H
SMe
H
X204
NEt2






950


embedded image




embedded image


H
Me
H
X205
OMe






951


embedded image




embedded image


H
CH═CH2
H
X206
Bn






952


embedded image




embedded image


H


embedded image


H
X207
SH






953


embedded image




embedded image


Me
Ac
H
X208
F






954


embedded image




embedded image


SPh
CO2Et
H
X209
Cl






955


embedded image




embedded image


H
COPh
H
X210
Br






956


embedded image




embedded image


H
H
Me
X211
CN






957


embedded image




embedded image


H
CONH2
H
X212
NO2






958


embedded image




embedded image


H
H
H
X213
OH






959


embedded image




embedded image


H
H
H
X214
NEt2






960


embedded image




embedded image


OCF3
H
H
X215
OMe






961


embedded image




embedded image


Me
H
H
X216
Bn






962


embedded image




embedded image


NO2
H
H
X217
SH






963


embedded image




embedded image


H
H
H
X218
SMe






964


embedded image




embedded image


H
H
H
X219
OMe






965


embedded image




embedded image


CN
H
H
X220
Bn






966


embedded image




embedded image


H
H
H
X221
SH






967


embedded image




embedded image


H
H
H
X222
SMe






968


embedded image




embedded image


H
H
H
X223
Me






969


embedded image




embedded image


OCF3
H
H
X224
CH═CH2






970


embedded image


—CN
Me
H
H
X225


embedded image











971


embedded image


—CH═NOH
NO2
H
H
X226
Ac






972


embedded image


—CH═NOCH2Ph
H
H
H
X227
CO2Et






973


embedded image




embedded image


CONH2
F
H
CO2Et
X231






974


embedded image




embedded image


H
Cl
H
SMe
X232






975


embedded image




embedded image


H
Br
H
Br
X233






976


embedded image




embedded image


H
CN
H
Me
X234






977


embedded image




embedded image


H
NO2
H
Et
X235






978


embedded image




embedded image


H
OH
Me
Me
X236






979


embedded image




embedded image


H
NEt2
SPh
H
X237






980


embedded image




embedded image


H
OMe
H
H
X238






981


embedded image




embedded image


H
Bn
H
Cl
X239






982


embedded image




embedded image


H
SH
H
NEt2
X240






983


embedded image




embedded image


H
SMe
H
H
X241






984


embedded image




embedded image


H
Me
H
H
X242






985


embedded image




embedded image


H
CH═CH2
OCF3
H
X243






986


embedded image




embedded image


H


embedded image


Me
H
X244






987


embedded image




embedded image


H
Ac
NO2
H
X245






988


embedded image




embedded image


H
CO2Et
H
H
X246






989


embedded image




embedded image


H
COPh
H
H
X247






990


embedded image




embedded image


H
H
CN
H
X248






991


embedded image




embedded image


CONEt2
CONH2
H
H
X249






992


embedded image




embedded image


Me
H
CO2Et
H
X250






993


embedded image




embedded image


NO2
H
SMe
H
X251






994


embedded image




embedded image


H
H
Br
H
X252






995


embedded image




embedded image


H
H
Me
H
X253






996


embedded image




embedded image


CN
H
Et
H
X254






997


embedded image


—CN
H
Me
Me
H
X255






998


embedded image


—CH═NOH
CF3
SPh
H
H
X256






999


embedded image


—CH═NOCH2Ph
CN
H
H
Me
X257






1000


embedded image




embedded image


X261
H
H
H
Cl






1001


embedded image




embedded image


X302
OCF3
H
H
CO2Et






1002


embedded image




embedded image


F
H
CO2Et
N001
H






1003


embedded image




embedded image


Cl
H
SMe
N002
H






1004


embedded image




embedded image


Br
H
Br
N003
H






1005


embedded image




embedded image


CN
H
Me
N004
H






1006


embedded image




embedded image


NO2
H
Et
N005
H






1007


embedded image




embedded image


OH
Me
Me
N006
H






1008


embedded image




embedded image


NEt2
SPh
H
N007
H






1009


embedded image




embedded image


OMe
H
H
S001
H






1010


embedded image




embedded image


Bn
H
Cl
S002
H






1011


embedded image




embedded image


SH
H
NEt2
S003
H






1012


embedded image




embedded image


SMe
H
H
S004
H






1013


embedded image




embedded image


Me
H
H
S005
H






1014


embedded image




embedded image


CH═CH2
OCF3
H
S006
H






1015


embedded image




embedded image




embedded image


Me
H
S007
H






1016


embedded image




embedded image


Ac
NO2
H
S008
H






1017


embedded image




embedded image


CO2Et
H
H
S009
H






1018


embedded image




embedded image


COPh
H
H
H001
H






1019


embedded image




embedded image


H
CN
H
H002
H






1020


embedded image




embedded image


CONH2
H
H
H003
H






1021


embedded image




embedded image


T001
CF3
H
Br
H






1022


embedded image




embedded image


T002
OiPr
H
H
H


















1023


embedded image




embedded image


T003
OCONH
H
H



















1024


embedded image


—CN
T004
Bn
H
H
H






1025


embedded image


—CH═NOH
T005
NEt2
H
H
H






1026


embedded image


—CH═NOCH2Ph
T006
OH
H
H
H






1027


embedded image




embedded image


Me
T010
F
H
CO2Et






1028


embedded image




embedded image


F
T011
Cl
H
SMe






1029


embedded image




embedded image


Cl
T012
Br
H
Br






1030


embedded image




embedded image


Br
T013
CN
H
Me






1031


embedded image




embedded image


CN
T014
NO2
H
Et






1032


embedded image




embedded image


H
T015
OH
Me
Me






1033


embedded image




embedded image


Me
T016
NEt2
SPh
H






1034


embedded image




embedded image


F
T017
OMe
H
H






1035


embedded image




embedded image


CF3
T018
Bn
H
Cl






1036


embedded image




embedded image


CO2Me
T019
SH
H
NEt2






1037


embedded image




embedded image


F
H004
SMe
H
H






1038


embedded image




embedded image


Cl
H005
Me
H
H






1039


embedded image




embedded image


H
H006
CH═CH2
OCF3
H






1040


embedded image




embedded image


H
H007


embedded image


Me
H






1041


embedded image




embedded image


H
X101
Ac
NO2
H






1042


embedded image




embedded image


CO2Et
X102
CO2Et
H
H






1043


embedded image




embedded image


Et
X103
COPh
H
H






1044


embedded image




embedded image


iPr
X104
H
CN
H






1045


embedded image




embedded image


Me
X105
CONH2
H
H






1046


embedded image




embedded image


Bn
X106
Cl
Me
Bn






1047


embedded image




embedded image


SH
X107
NEt2
F
NEt2






1048


embedded image




embedded image


SMe
X108
H
Cl
OH






1049


embedded image




embedded image


Me
X109
H
Br
Br






1050


embedded image




embedded image


CH═CH2
X110
H
CN
Cl






1051


embedded image


—CN


embedded image


X111
H
H
F






1052


embedded image


—CH═NOH
Ac
X112
H
Me
SH






1053


embedded image


—CH═NOCH2Ph
CO2Et
X113
H
F
SMe






1054


embedded image




embedded image


H
Ac
X117
Cl
H






1055


embedded image




embedded image


H
CO2Et
X118
H
H






1056


embedded image




embedded image


Cl
COPh
X119
H
H






1057


embedded image




embedded image


NEt2
H
X120
H
H






1058


embedded image




embedded image


H
CONH2
X121
CO2Et
H






1059


embedded image




embedded image


H
H
X122
Et
H






1060


embedded image




embedded image


H
H
X123
iPr
H






1061


embedded image




embedded image


H
H
X124
Me
H






1062


embedded image




embedded image


H
H
X125
Me
Me






1063


embedded image




embedded image


H
H
X126
F
F






1064


embedded image




embedded image


H
H
X127
CF3
Cl






1065


embedded image




embedded image


H
H
X128
CO2Me
Br






1066


embedded image




embedded image


H
H
X129
F
CN






1067


embedded image




embedded image


H
H
X130
Cl
H






1068


embedded image




embedded image


H
H
X131
H
Me






1069


embedded image




embedded image


H
H
X132
H
F






1070


embedded image




embedded image


H
H
X133
H
CF3






1071


embedded image




embedded image


H
H
X134
CO2Et
CO2Me






1072


embedded image




embedded image


H
H
X135
Et
H






1073


embedded image




embedded image


H
H
X136
iPr
H






1074


embedded image




embedded image


H
H
X137
Me
H






1075


embedded image




embedded image


H
H
X138
Me
H






1076


embedded image




embedded image


H
H
X139
F
H






1077


embedded image




embedded image


H
H
X140
CF3
H






1078


embedded image


—CN
H
H
X141
CO2Me
H






1079


embedded image


—CH═NOH
Br
F
X142
H
H






1080


embedded image


—CH═NOCH2Ph
H
Cl
X143
H
H






1081


embedded image




embedded image


H
OH
X147
H
F






1082


embedded image




embedded image


H
NEt2
X148
H
Cl






1083


embedded image




embedded image


H
OMe
H
X201
Br






1084


embedded image




embedded image


H
Bn
H
X202
CN






1085


embedded image




embedded image


H
SH
H
X203
OH






1086


embedded image




embedded image


H
SMe
H
X204
NEt2






1087


embedded image




embedded image


H
Me
H
X205
OMe






1088


embedded image




embedded image


H
CH═CH2
H
X206
Bn






1089


embedded image




embedded image


H


embedded image


H
X207
SH






1090


embedded image




embedded image


Me
Ac
H
X208
F






1091


embedded image




embedded image


SPh
CO2Et
H
X209
Cl






1092


embedded image




embedded image


H
COPh
H
X210
Br






1093


embedded image




embedded image


H
H
Me
X211
CN






1094


embedded image




embedded image


H
CONH2
H
X212
NO2






1095


embedded image




embedded image


H
H
H
X213
OH






1096


embedded image




embedded image


H
H
H
X214
NEt2






1097


embedded image




embedded image


OCF3
H
H
X215
OMe






1098


embedded image




embedded image


Me
H
H
X216
Bn






1099


embedded image




embedded image


NO2
H
H
X217
SH






1100


embedded image




embedded image


H
H
H
X218
SMe






1101


embedded image




embedded image


H
H
H
X219
OMe






1102


embedded image




embedded image


CN
H
H
X220
Bn






1103


embedded image




embedded image


H
H
H
X221
SH






1104


embedded image




embedded image


H
H
H
X222
SMe






1105


embedded image


—CN
H
H
H
X223
Me






1106


embedded image


—CH═NOH
OCF3
H
H
X224
CH═CH2






1107


embedded image


—CH═NOCH2Ph
Me
H
H
X225


embedded image








1108


embedded image




embedded image


CN
H
H
X229
H






1109


embedded image




embedded image


NO2
CONEt2
H
X230
H






1110


embedded image




embedded image


CONH2
F
H
CO2Et
X231






1111


embedded image




embedded image


H
Cl
H
SMe
X232






1112


embedded image




embedded image


H
Br
H
Br
X233









1113


embedded image




embedded image


H
CN
H
Me
X234






1114


embedded image




embedded image


H
NO2
H
Et
X235






1115


embedded image




embedded image


H
OH
Me
Me
X236






1116


embedded image




embedded image


H
NEt2
SPh
H
X237






1117


embedded image




embedded image


H
OMe
H
H
X238






1118


embedded image




embedded image


H
Bn
H
Cl
X239






1119


embedded image




embedded image


H
SH
H
NEt2
X240






1120


embedded image




embedded image


H
SMe
H
H
X241






1121


embedded image




embedded image


H
Me
H
H
X242






1122


embedded image




embedded image


H
CH═CH2
OCF3
H
X243






1123


embedded image




embedded image


H


embedded image


Me
H
X244






1124


embedded image




embedded image


H
Ac
NO2
H
X245






1125


embedded image




embedded image


H
CO2Et
H
H
X246






1126


embedded image




embedded image


H
COPh
H
H
X247






1127


embedded image




embedded image


H
H
CN
H
X248






1128


embedded image




embedded image


CONEt2
CONH2
H
H
X249






1129


embedded image




embedded image


Me
H
CO2Et
H
X250






1130


embedded image




embedded image


NO2
H
SMe
H
X251






1131


embedded image




embedded image


H
H
Br
H
X252






1132


embedded image


—CN
H
H
Me
H
X253






1133


embedded image


—CH═NOH
CN
H
Et
H
X254






1134


embedded image


—CH═NOCH2Ph
H
Me
Me
H
X255






1135


embedded image




embedded image


Br
H
NEt2
H
X259






1136


embedded image




embedded image


CF3
H
H
H
X260






1137


embedded image




embedded image


X261
H
H
H
Cl






1138


embedded image




embedded image


X302
OCF3
H
H
CO2Et






1139


embedded image




embedded image


F
H
CO2Et
N001
H






1140


embedded image




embedded image


Cl
H
SMe
N002
H






1141


embedded image




embedded image


Br
H
Br
N003
H






1142


embedded image




embedded image


CN
H
Me
N004
H






1143


embedded image




embedded image


NO2
H
Et
N005
H






1144


embedded image




embedded image


OH
Me
Me
N006
H






1145


embedded image




embedded image


NEt2
SPh
H
N007
H






1146


embedded image




embedded image


OMe
H
H
S001
H






1147


embedded image




embedded image


Bn
H
Cl
S002
H






1148


embedded image




embedded image


SH
H
NEt2
S003
H






1149


embedded image




embedded image


SMe
H
H
S004
H






1150


embedded image




embedded image


Me
H
H
S005
H






1151


embedded image




embedded image


CH═CH2
OCF3
H
S006
H






1152


embedded image




embedded image




embedded image


Me
H
S007
H






1153


embedded image




embedded image


Ac
NO2
H
S008
H






1154


embedded image




embedded image


CO2Et
H
H
S009
H






1155


embedded image




embedded image


COPh
H
H
H001
H






1156


embedded image




embedded image


H
CN
H
H002
H






1157


embedded image




embedded image


CONH2
H
H
H003
H






1158


embedded image




embedded image


T001
CF3
H
Br
H






1159


embedded image


—CN
T002
OiPr
H
H
H


















1160


embedded image


—CH═NOH
T003
OCONH
H
H



















1161


embedded image


—CH═NOCH2Ph
T004
Bn
H
H
H






1162


embedded image




embedded image


T008
Cl
H
H
H






1163


embedded image




embedded image


T009
F
H
H
H






1164


embedded image




embedded image


Me
T010
F
H
CO2Et






1165


embedded image




embedded image


F
T011
Cl
H
SMe






1166


embedded image




embedded image


Cl
T012
Br
H
Br






1167


embedded image




embedded image


Br
T013
CN
H
Me






1168


embedded image




embedded image


CN
T014
NO2
H
Et






1169


embedded image




embedded image


H
T015
OH
Me
Me






1170


embedded image




embedded image


Me
T016
NEt2
SPh
H






1171


embedded image




embedded image


F
T017
OMe
H
H






1172


embedded image




embedded image


CF3
T018
Bn
H
Cl






1173


embedded image




embedded image


CO2Me
T019
SH
H
NEt2






1174


embedded image




embedded image


F
H004
SMe
H
H






1175


embedded image




embedded image


Cl
H005
Me
H
H






1176


embedded image




embedded image


H
H006
CH═CH2
OCF3
H






1177


embedded image




embedded image


H
H007


embedded image


Me
H






1178


embedded image




embedded image


H
X101
Ac
NO2
H






1179


embedded image




embedded image


CO2Et
X102
CO2Et
H
H






1180


embedded image




embedded image


Et
X103
COPh
H
H






1181


embedded image




embedded image


iPr
X104
H
CN
H






1182


embedded image




embedded image


Me
X105
CONH2
H
H






1183


embedded image




embedded image


Bn
X106
Cl
Me
Bn






1184


embedded image




embedded image


SH
X107
NEt2
F
NEt2






1185


embedded image




embedded image


SMe
X108
H
Cl
OH






1186


embedded image


—CN
Me
X109
H
Br
Br






1187


embedded image


—CH═NOH
CH═CH2
X110
H
CN
Cl






1188


embedded image


—CH═NOCH2Ph


embedded image


X111
H
H
F






1189


embedded image




embedded image


H
X115
H
CO2Me
CH═CH2






1190


embedded image




embedded image


CONH2
X116
H
F


embedded image








1191


embedded image




embedded image


H
Ac
X117
Cl
H






1192


embedded image




embedded image


H
CO2Et
X118
H
H






1193


embedded image




embedded image


Cl
COPh
X119
H
H






1194


embedded image




embedded image


NEt2
H
X120
H
H






1195


embedded image




embedded image


H
CONH2
X121
CO2Et
H






1196


embedded image




embedded image




embedded image


H
X122
Et
H






1197


embedded image




embedded image


H


embedded image


X123
iPr
H






1198


embedded image




embedded image


H
H
X124
Me
H






1199


embedded image




embedded image


H


embedded image


X125
Me
Me






1200


embedded image




embedded image


H
H
X126
F
F






1201


embedded image




embedded image


H
H
X127
CF3
Cl






1202


embedded image




embedded image


H
H
X128
CO2Me
Br






1203


embedded image




embedded image


H
H
X129
F
CN






1204


embedded image




embedded image


OPh
H
X130
Cl
H






1205


embedded image




embedded image


Pyridin-2-yl
H
X131
H
Me






1206


embedded image




embedded image




embedded image


H
X132
H
F






1207


embedded image




embedded image




embedded image


H
X133
H
CF3






1208


embedded image




embedded image




embedded image


H
X134
CO2Et
CO2Me






1209


embedded image




embedded image




embedded image


H
X135
Et
H






1210


embedded image




embedded image


H
H
X136
iPr
H






1211


embedded image




embedded image


H
H
X137
Me
SPh






1212


embedded image




embedded image


H
H
X138
Me
SOPh






1213


embedded image


—CN
H
H
X139
F
SO2Ph






1214


embedded image


—CH═NOH
H
H
X140
CF3
SOMe






1215


embedded image


—CH═NOCH2Ph
H
H
X141
CO2Me
SO2Et






1216


embedded image




embedded image


H
CN
X145
H
H






1217


embedded image




embedded image


H
NO2
X146
H
H






1218


embedded image




embedded image


H
OH
X147
H
F






1219


embedded image




embedded image


H
NEt2
X148
H
Cl






1220


embedded image




embedded image


H
OMe
H
X201
Br






1221


embedded image




embedded image


H
Bn
H
X202
CN






1222


embedded image




embedded image


H
SH
H
X203
OH






1223


embedded image




embedded image


H
SMe
H
X204
NEt2






1224


embedded image




embedded image


H
Me
H
X205
OMe






1225


embedded image




embedded image


H
CH═CH2
H
X206
Bn






1226


embedded image




embedded image


H


embedded image


H
X207
SH






1227


embedded image




embedded image


Me
Ac
H
X208
F






1228


embedded image




embedded image


SPh
CO2Et
H
X209
Cl






1229


embedded image




embedded image


H
COPh
H
X210
Br






1230


embedded image




embedded image


H
H
Me
X211
CN






1231


embedded image




embedded image


H
CONH2
H
X212
NO2






1232


embedded image




embedded image


SMe
H
H
X213
OH






1233


embedded image




embedded image


H
SH
H
X214
NEt2






1234


embedded image




embedded image


OCF3
H
H
X215
OMe






1235


embedded image




embedded image


Me
H
H
X216
Bn






1236


embedded image




embedded image


NO2
H
H
X217
SH






1237


embedded image




embedded image


H
H
CSPh
X218
SMe






1238


embedded image




embedded image


H


embedded image


H
X219
OMe






1239


embedded image




embedded image


CN
H
H
X220
Bn






1240


embedded image


—CN
H
H
CSCH═CH2
X221
SH






1241


embedded image


—CH═NOH
COPh
H
H
X222
SMe






1242


embedded image


—CH═NOCH2Ph
H
CSMe
H
X223
Me






1243


embedded image




embedded image


H
H
H
X227
CO2Et






1244


embedded image




embedded image


H
H
H
X228
COPh






1245


embedded image




embedded image


CN
H
H
X229
H






1246


embedded image




embedded image


NO2
CONEt2
H
X230
H






1247


embedded image




embedded image


CONH2
F
H
CO2Et
X231






1248


embedded image




embedded image


H
Cl
H
SMe
X232






1249


embedded image




embedded image


H
Br
H
Br
X233






1250


embedded image




embedded image


H
CN
H
Me
X234






1251


embedded image




embedded image


H
NO2
H
Et
X235






1252


embedded image




embedded image


H
OH
Me
Me
X236






1253


embedded image




embedded image


H
NEt2
SPh
H
X237






1254


embedded image




embedded image


H
OMe
H
H
X238






1255


embedded image




embedded image


H
Bn
H
Cl
X239






1256


embedded image




embedded image


H
SH
H
NEt2
X240






1257


embedded image




embedded image


H
SMe
H
H
X241






1258


embedded image




embedded image


COCH═CH2
Me
H
H
X242






1259


embedded image




embedded image


H
CH═CH2
OCF3
H
X243






1260


embedded image




embedded image


H


embedded image


Me
H
X244






1261


embedded image




embedded image


H
Ac
NO2
H
X245






1262


embedded image




embedded image


H
CO2Et
H
H
X246






1263


embedded image




embedded image


H
COPh
H
H
X247






1264


embedded image




embedded image


H
4-Cl—Ph
CN
H
X248






1265


embedded image




embedded image


CONEt2
Et
H
H
X249






1266


embedded image




embedded image


Me
H
CO2Et
H
X250









In Table 3, compounds with compound numbers 229 and 230 are cis-trans isomers based on the configuration of the 3,5-dimethyl group in the 3,5-dimethyl-piperidine-1-yl group of G in the aforementioned formula (1), and compounds with compound numbers 267 and 268 are cis-trans isomers based on the configuration of the 3,4-difluoro group in the 3,4-difluoropyrrolidine-1-yl group. Moreover, 1H-NMR. data on several compounds in Table 3 are shown in Table 4 below. Note that compound numbers in Table 4 correspond to those in Table 3.










TABLE 4





Compound



No.
















12

1H-NMR (CDCl3, δ ppm): 1.79 (s, 6H), 2.04-2.09 (m, 4H),




2.90-3.15 (m, 6H), 3.61 (br s, 2H), 3.80 (br s, 2H),



7.52 (d, 1H), 7.78 (d, 1H)


40

1H-NMR (CDCl3, δ ppm): 1.96-2.12 (m, 4H), 2.89 (s, 3H),




3.12 (s, 3H), 3.58 (br s, 2H), 3.76 (br s, 2H), 6.90 (d, 1H),



7.18 (s, 1H)


46

1H-NMR (CDCl3, δ ppm): 1.36 (s, 9H), 2.02-2.08 (m, 4H),




2.22 (s, 1H), 3.60 (br s, 2H), 3.76 (br s, 2H), 4.04 (d, 1H),



4.71 (d, 1H), 7.00 (d,1H), 7.21 (d, 1H)


57

1H-NMR (CDCl3, δ ppm): 1.57 (s, 6H), 2.02-2.08 (m, 4H),




3.60 (br s, 2H), 3.71 (br s, 2H), 6.72 (d, 1H), 7.13 (d, 1H)


71

1H-NMR (CDCl3, δ ppm): 1.24 (t, 3H), 2.02-2.08 (m, 4H),




3.60 (bs, 2H), 3.78 (bs, 2H), 4.22 (q, 2H), 6.14 (s, 1H),



7.25 (d, 1H), 7.41 (m, 3H), 7.57 (d, 2H), 7.70 (d, 1H)


72

1H-NMR (CDCl3, δ ppm): 1.73 (s, 6H), 2.03-2.08 (m, 4H),




3.60 (br s, 2H), 3.80 (br s, 2H), 7.23 (d, 1H),



7.57 (d, 1H)


78

1H-NMR (CDCl3, δ ppm): 1.82(s, 6H), 2.04-2.09 (m, 4H),




3.60 (br s, 2H), 3.78 (br s, 2H), 5.49 (br s, 1H),



6.35 (br s, 1H), 7.23 (d, 1H), 7.50 (d, 1H)


80

1H-NMR (CDCl3, δ ppm): 1.16 (t, 3H), 1.80 (s, 6H),




2.05-2.09 (m, 4H), 3.34 (dq, 2H), 3.60 (bs, 1H),



3.78 (bs, 1H), 6.48 (bt, 1H), 7.23 (d, 1H), 7.49 (d, 1H)


86

1H-NMR (CDCl3, δ ppm): 1.83 (s, 6H), 2.04-2.08 (m, 4H),




3.59 (br s, 2H), 3.74 (br s, 2H), 4.49 (d, 2H), 6.78 (br t, 1H),



7.18 (d, 1H), 7.26-7.36 (m, 5H), 7.47 (d, 1H)


88

1H-NMR (CDCl3, δ ppm): 1.91 (s, 6H), 2.05-20.9 (m, 4H),




3.60 (bs, 2H), 3.78 (bs, 2H), 6.65 (s, 1H), 7.23-7.37 (m, 5H),



7.52-7.60 (m, 2H)


89

1H-NMR (CDCl3, δ ppm): 1.80 (s, 1H), 2.02-2.08 (m, 4H),




3.58 (bs, 2H), 3.74 (bs, 2H), 7.19 (d, 1H), 7.61-7.69 (m, 3H),



7.90 (t, 1H), 8.63 (d, 2H)


90

1H-NMR (CDCl3, δ ppm): 1.83 (s, 6H), 2.05-2.10 (m, 4H),




3.60 (br s, 2H), 3.73-3.80 (m, 5H), 7.24 (d, 1H),



7.49 (d, 1H), 9.03 (s, 1H)


92

1H-NMR (CDCl3, δ ppm): 1.73 (s, 6H), 2.05-2.10 (m, 4H),




2.96-3.09 (m, 6H), 3.60 (br s, 2H), 3.78 (br s, 2H),



7.24 (d, 1H), 7.55 (d, 1H)


97

1H-NMR (CDCl3, δ ppm): 1.74 (s, 6H), 2.05-2.09 (m, 4H),




3.18 (s, 3H), 3.60 (bs, 2H), 3.79 (bs, 2H), 4.36 (s, 2H),



7.25 (d, 1H), 7.55 (d, 1H)


109

1H-NMR (CDCl3, δ ppm): 1.30 (t, 3H), 1.73 (s, 6H),




2.07(m, 4H), 3.60 (br, 2H), 3.77 (br, 2H), 4.24 (q, 2H),



7.21 (d, 1H), 7.51 (d, 1H), 7.62 (br, 1H), 7.86 (br, 1H)


110

1H-NMR (CDCl3, δ ppm): 1.37-1.48 (m, 2H),




1.67-1.78 (m, 2H), 1.96-2.11 (m, 4H), 3.59 (br s, 2H),



3.77 (br s, 2H), 4.26 (br s, 1H) 7.23 (d, 1H), 7.61 (d, 1H)


115

1H-NMR (CDCl3, δ ppm): 1.97 (s, 3H), 2.07 (m, 4H),




3.67 (br, 2H), 3.79 (br, 2H), 7.26 (d, 1H), 7.62 (d, 1H)


116

1H-NMR (CDCl3, δ ppm): 1.14 (t, 3H), 1.98 (s, 3H),




2.08 (m, 4H), 3.36 (m, 2H), 3.61 (br S, 2H), 3.79 (br s, 2H),



6.04 (br s, 1H), 7.26 (d, 1H), 7.57 (d, 1H)


117

1H-NMR (CDCl3, δ ppm): 1.99 (s, 3H), 2.08 (m, 4H),




3.05 (br, 6H), 3.61 (br, 2H), 3.79 (br, 2H), 7.28 (d, 1H),



7.60 (d, 1H)


118

1H-NMR (CDCl3, δ ppm): 1.04 (t, 3H), 1.72 (s, 3H),




1.93-2.22 (m, 6H), 3.60 (br s, 2H), 3.77 (br s, 2H),



5.30 (br s, 1H), 7.22 (d, 1H), 7.56 (d, 1H)


122

1H-NMR (CDCl3, δ ppm): 0.96 (t, 6H), 1.96-2.33 (m, 8H),




3.60 (br s, 2H), 3.77 (br s, 2H), 5.41 (br s, 1H),



7.22 (d, 1H), 7.58 (d, 1H)


144

1H-NMR (CDCl3, δ ppm): 2.05 (br, 4H), 2.59 (s, 1H),




3.52 (br, 2H), 3.78 (br, 2H), 4.80 (s, 2H), 7.32 (d, 1H)


168
1H-NMR (CDCl3, δ ppm): 1.52 (s, 6H), 2.05 (m, 4H),



2.96 (s, 2H), 3.58 (br, 2H), 3.72 (br, 2H), 6.94 (d, 1H)


184

1H-NMR (CDCl3, δ ppm): 2.05-2.09 (m, 4H), 2.56 (t, 1H),




3.60-3.75 (m, 4H), 4.75 (d, 2H), 6.69 (s, 1H), 7.42 (s, 1H)


187

1H-NMR (CDCl3, δ ppm): 2.02-2.07 (m, 8H),




3.62 (br s, 4H), 3.72 (br s, 4H), 6.57 (s, 1H), 7.45 (s, 1H)


188

1H-NMR (CDCl3, δ ppm): 1.81-1.87 (m, 4H), 2.03-2.09




(m, 4H). 3.36-3.42 (m, 4H), 3.57 (br s, 2H), 3.80 (br s, 2H),



3.81-3.85 (m, 2H), 4.90-4.92 (m, 1H), 5.20-5.32 (m, 2H),



6.85-5.98 (m, 1H), 6.60 (s, 1H), 7.49 (s, 1H)


192

1H-NMR (CDCl3, δ ppm): 1.88-1.93 (m, 4H), 3.54 (br s, 4H),




5.10 (s, 2H), 6.50 (d, 1H), 6.95 (d, 1H), 7.24-7.39 (m, 5H),



7.60 (s, 1H)


199

1H-NMR (CDCl3, δ ppm): 2.00 (br m, 4H), 2.52 (t, 1H),




2.79 (s, 3H), 2.85 (s, 3H), 3.10-3.30 (br m, 1H),



3.50-3.80 (br m, 3H), 4.66 (d, 2H), 6.70 (d, 1H), 7.04 (d, 1H)


201

1H-NMR (CDCl3, δ ppm): 1.24 (t, 3H), 1.64 (s, 6H),




1.97 (br s, 4H), 2.17 (s, 3H), 3.20-3.73 (br m, 4H),



4.20(q, 2H), 7.05 (d, 1H), 7.26 (d, 1H), 9.62 (br s, 1H)


204

1H-NMR (CDCl3, δ ppm): 1.24 (t, 3H), 1.66 (s, 6H),




1.75-2.25 (br m, 4H), 3.07 (s, 3H), 3.07-3.85 (br m, 4H),



4.17 (q, 2H), 4.34 (d, 1H), 5.72 (d, 1H), 6.88 (dd, 2H),



6.94 (d, 1H), 7.24 (m, 3H), 7.80 (d, 1H)


205

1H-NMR (CDCl3, δ ppm): 1.80-2.05 (br m, 8H), 2.52 (t, 1H),




3-3.8 (br m, 8H), 4.67 (d, 2H), 7.00 (d, 1H), 7.03 (d, 1H)


208

1H-NMR (CDCl3, δ ppm): 1.70-2.05 (m, 4H), 2.35 (d, 3H),




2.50 (t, 1H), 3.37 (br s, 2H), 3.68 (br s, 2H), 4.58 (d, 2H),



5.71 (s, 1H), 6.48 (d, 1H), 6.94 (d, 1H)


209

1H-NMR (CDCl3, δ ppm): 1.92-2.03 (m, 4H), 2.47 (t, 1H),




3.56 (br s, 4H), 4.53 (d, 2H), 6.44 (d, 1H), 6.93 (d, 1H),



7.38 (d, 1H), 7.82 (d, 1H)


210

1H-NMR (CDCl3, δ ppm): 1.90-2.07 (br m, 4H), 2.45 (t, 1H),




3.23, 3.74 (br s, 4H), 4.48 (d, 2H), 6.38 (d, 1H), 6.87 (d, 1H),



7.08 (d, 1H), 7.20 (m, 1H), 7.54 (t, 1H), 8.61 (m, 1H)


252

1H-NMR (CDCl3, δ ppm): 1.60 (s, 9H), 3.73-3.84 (m, 8H),




7.30 (d, 1H), 7.42 (d, 1H)


258

1H-NMR (CDCl3, δ ppm): 1.16 (t, 3H), 1.80 (s, 6H),




3.35 (m, 2H), 4.18 (br m, 4H), 6.39 (br s, 1H), 7.28 (d, 1H),



7.51 (d, 1H)


264

1H-NMR (CDCl3, δ ppm): 1.16 (t, 3H), 1.80 (s, 6H),




3.34 (dq, 2H), 3.70-3.83 (m, 8H), 6.47 (bt, 1H), 7.24 (d, 1H),



7.48 (d, 1H)


267

1H-NMR (CDCl3, δ ppm): 2.57 (t, 1H), 4.08 (br m, 4H),




4.74 (d, 2H), 5.20-5.40 (m, 2H), 6.74 (d, 1H), 7.19 (d, 1H)


268

1H-NMR (CDCl3, δ ppm): 2.57 (t, 1H), 4.01 (br m, 4H),




4.73 (d, 2H), 5.15-5.37 (m, 2H), 6.72 (d, 1H), 7.19 (d, 1H)


284

1H-NMR (CDCl3, δ ppm): 2.05 (m, 4H), 3.58 (br, 2H),




3.77 (br, 2H), 3.81 (s, 3H), 6.79 (br, 1H), 7.22 (d, 1H),



7.40 (d, 1H), 7.94 (br, 1H)


285

1H-NMR (CDCl3, δ ppm): 2.08 (m, 4H), 3.60 (br, 2H),




3.79 (br, 2H), 7.30 (d, 1H), 7.46 (d, 1H), 8.99 (br, 1H)


292

1H-NMR (CDCl3, δ ppm): 2.07 (m, 4H), 3.15 (s, 6H),




3.60 (br, 2H), 3.78 (br, 2H), 7.30 (d, 1H), 7.79 (d, 1H)


296

1H-NMR (CDCl3, δ ppm): 2.51 (tt, 2H), 4.28 (t, 4H),




6.86 (d, 1H), 7.19 (dd, 1H), 7.41 (d, 1H)


302

1H-NMR (CDCl3, δ ppm): 2.26 (t, 1H), 3.96 (d, 2H),




4.12 (m, 4H), 4.42 (br s, 1H), 6.36 (d, 1H), 7.13 (d, 1H)


303

1H-NMR (CDCl3, δ ppm): 2.04 (m, 4H), 3.58 (br, 2H),




3.76 (br, 2H), 3.82 (s, 3H), 4.06 (m, 2H), 4.85 (m, 1H),



7.21 (d, 1H), 7.30 (br, 1H), 7.42 (d, 1H)


306

1H-NMR (CDCl3, δ ppm): 2.06 (m, 4H), 2.31 (t, 1H),




3.58 (br, 2H), 3.76 (br, 2H), 4.08 (m, 2H), 4.91 (m, 1H),



5.26 (s, 2H), 7.20 (d, 1H), 7.32 (m, 5H), 7.40 (d, 1H)


311

1H-NMR (CDCl3, δ ppm): 2.05 (m, 4H), 3.57 (m, 2H),




3.75 (br, 2H), 4.61 (m, 2H), 4.99 (dd, 1H), 5.25 (s, 2H),



7.22 (d, 1H), 7.35 (m, 5H), 7.51 (d, 1H)


314

1H-NMR (CDCl3, δ ppm): 1.28 (t, 3H), 2.04 (m, 4H),




3.59 (br, 2H), 3.76 (br, 2H), 4.30 (q, 2H),



7.15 (d, 1H), 7.29 (d, 1H), 7.97 (s, 1H)


318

1H-NMR (CDCl3, δ ppm): 2.06 (m, 4H), 3.58 (br, 2H),




3.76 (br, 2H), 5.40 (s, 2H), 7.27 (d, 1H),



7.38 (m, 5H), 7.73 (d, 1H), 8.33 (s, 1H)


321

1H-NMR (CDCl3, δ ppm): 1.25 (t, 3H), 2.03 (m, 4H),




3.49 (m, 3H), 3.58 (br, 2H), 3.75 (br, 2H), 4.12 (q, 2H),



6.18 (br, 1H), 7.17 (d, 1H), 7.33 (d, 1H)


325

1H-NMR (CDCl3, δ ppm): 2.12-2.22 (m, 2H), 2.56 (t, 1H),




3.63 (br t, 2H), 3.87 (br s, 2H), 4.74 (d, 2H),



6.54 (d, 1H), 7.05 (m, 3H), 7.15 (d, 1H), 7.33 (m, 2H)


326

1H-NMR (CDCl3, δ ppm): 2.53 (t, 1H), 2.82 (t, 2H),




4.10 (t, 2H), 4.69 (t, 2H), 6.68 (d, 1H),



7.01-7.42 (m, 6H)


334

1H-NMR (CDCl3, δ ppm): 1.25 (m, 3H), 3.50 (m, 2H),




4.15 (br s, 4H), 6.22 (br s, 1H), 7.22 (d, 1H), 7.38 (d, 1H)


336

1H-NMR (CDCl3, δ ppm): 1.47 (t, 3H), 4.16 (br, 4H),




4.54 (q, 2H), 7.36 (d, 1H), 7.53 (d, 1H)


337

1H-NMR (CDCl3, δ ppm): 3.15 (s, 6H), 4.18 (br, 4H),




7.36 (d, 1H), 7.52 (d, 1H)


339

1H-NMR (CDCl3, δ ppm): 4.08 (br m, 4H), 5.07 (s, 2H),




6.41 (d, 1H), 6.93-7.15 (m, 4H), 7.25-7.32 (m, 6H)


398

1H-NMR (CDCl3): δ 0.90 (t, 3H), 1.68 (m, 2H),




2.06 (m, 4H), 2.52 (t, 2H), 3.77 (br, 2H), 3.85 (br, 2H),



6.99 (d, 1H), 7.27 (d, 1H), 7.89 (s, 1H)


406

1H-NMR (CDCl3): δ 1.99 (s, 6H), 2.07 (m, 4H),




3.59 (br, 2H), 3.77 (br, 2H), 7.22 (d, 1H),



7.54 (d, 1H), 8.36 (s, 1H)


408

1H-NMR (CDCl3): δ 1.91 (s, 6H), 2.06 (m, 4H),




3.59 (br, 2H), 3.77 (br, 2H), 7.21 (d, 1H),



7.24-7.46 (m, 5H), 7.53 (d, 1H)


415

1H-NMR (CDCl3): δ 1.72 (d, 3H), 2.03 (m, 4H),




3.54 (br, 2H), 3.72 (br, 2H), 5.29 (s, 2H), 5.52 (q, 1H),



6.62 (d, 1H), 6.79 (s, 1H), 6.99-7.02 (m, 3H),



7.10 (d, 1H), 7.26-29 (m, 3H)


417

1H-NMR (CDCl3): δ 1.75 (s, 6H), 2.08 (m, 4H), 3.16 (s, 3H),




3.60 (br, 2H), 3.78 (br, 2H), 4.05 (q, 2H), 7.24 (d, 1H),



7.55 (d, 1H)


423

1H-NMR (CDCl3): δ 1.91 (s, 6H), 2.07 (m, 4H), 2.40 (s, 3H),




3.59 (br, 2H), 3.77 (br, 2H), 6.02 (s, 1H), 7.21 (d, 1H),



7.51 (d, 1H)


429

1H-NMR (CDCl3): δ 1.47 (d, 3H), 1.60 (m, 3H), 2.06 (m,




4H), 3.60 (br, 2H), 3.75 (br, 2H), 5.07 (m, 1H), 6.52



(d, 1H), 7.14 (d, 1H)


430

1H-NMR (CDCl3): δ 1,18 (t, 3H), 2.57 (t, 1H), 3.34 (q, 1H),




3.66-3.85 (br, 2H), 4.09-4.28 (br, 5H), 4.73 (d, 2H),



6.74 (d, 1H), 7.18 (d, 1H), 7.29 (m, 5H)


432

1H-NMR (CDCl3): δ 1.92 (s, 6H), 2.06 (m, 4H), 3.59 (br,




2H), 3.76 (br, 2H), 7.19 (d, 1H), 7.52 (d, 1H), 7.70 (s, 1H),



7.83 (s, 1H)


434

1H-NMR (CDCl3): δ 1.92 (s, 6H), 2.07 (m, 4H), 2.29 (s, 3H),




3.60 (br, 2H), 3.77 (br, 2H), 6.09 (s, 1H), 7.21 (d, 1H),



7.52 (d, 1H)


436

1H-NMR (CDCl3): δ 2.08-2.43 (m, 4H), 2.56 (t, 1H),




3.76 (s, 3H), 3.60-3.95 (m, 2H), 4.54 (br, 1H),



4.72 (d, 2H), 6.68 (d, 1H), 7.15 (d, 1H)


437

1H-NMR (CDCl3): δ 1.79 (s, 6H), 2.07 (m, 4H), 3.37 (s, 6H),




3.44 (d, 2H), 3.60 (br, 2H), 3.78 (br, 2H), 4.39 (t, 1H),



6.59 (br, 1H), 7.23 (d, 1H), 7.52 (d, 1H)


440

1H-NMR (CDCl3): δ 0.37 (m, 2H), 0.63 (m, 2H),




1.28 (m, 1H), 2.05 (m, 4H), 3.58 (br, 2H), 3.74 (br, 2H),



3.84 (d, 2H), 6.56 (d, 1H), 7.15 (d, 1H)


442

1H-NMR (CDCl3): δ 1.74 (s, 6H), 2.03 (m, 4H), 2.31 (s, 3H),




3.54 (br, 2H), 3.71 (br, 2H), 6.10 (s, 1H), 6.28 (d, 1H),



7.13 (d, 1H)


443

1H-NMR (CDCl3): δ 1.88 (s, 6H), 2.07 (m, 4H), 3.60




(br, 2H), 3.78 (br, 2H), 7.23 (d, 1H), 7.31 (d, 2H), 7.52



(d, 1H), 8.58 (d, 2H)


451

1H-NMR (CDCl3): δ 2.03 (m, 6H), 2.07 (m, 4H),




3.60 (br, 2H),3.78 (br, 2H), 7,23 (d, 1H), 7.45 (dd, 1H),



7.56 (d, 1H), 7.64 (dd, 1H), 9.10 (dd, 1H)


455

1H-NMR (CDCl3): δ 1.90 (s, 6H), 2.06 (m, 4H), 3.59




(br, 2H), 3.77 (br, 2H), 7.09 (s, 1H), 7.20 (d, 1H),



7.47 (d, 1H), 7.82 (s, 1H)









[Herbicide]

Although a few examples regarding herbicides of the present invention are shown next, active-ingredient compounds, additives, and proportions added are changeable over a wide range without being limited solely to the present examples. Parts in Examples of formulations show parts by weight.


Formulation Example 1
Wettable Powder

















Compound of the present invention
20 parts



White carbon
20 parts



Diatomaceous earth
52 parts



Sodium alkyl sulfate
 8 parts









The above components were mixed homogenously and ground finely to obtain a wettable powder with 20% of active ingredient.


Formulation Example 2
Emulsion


















Compound of the present invention
 5 parts



Dimethylformamide
94 parts



polyoxyethylene-sorbitan type surfactant
 1 part










The above components were mixed and dissolved to obtain an emulsion with 5% of active ingredient.


Formulation Example 3
Emulsion


















Compound of the present invention
20 parts



Xylene
55 parts



Dimethylformamide
15 parts



Polyoxyethylene phenyl ether
10 parts










The above components were mixed and dissolved to obtain an emulsion with 20% of active ingredient.


Formulation Example 4
Granules


















Compound of the present invention
 5 parts



Talc
40 parts



Clay
38 parts



Bentonite
10 parts



Sodium alkyl sulfate
 7 parts










The above components were mixed homogenously and, after being ground finely, granulated to obtain granules with a diameter of 0.5 to 1.0 mm and 5% of active ingredient.


Test Examples regarding the effect of herbicides of the present invention are shown next.


Herbicidal effects were examined following the below examination criteria and are represented by the use of herbicidal index.


Examination Criteria
















Herbicidal rate
Herbicidal index



















0%
0



20-29%
2



40-49%
4



60-69%
6



80-89%
8



100% 
10










Additionally, numerical values 1, 3, 5, 7, and 9 respectively show intermediate values between 0 and 2, between 2 and 4, between 4 and 6, between 6 and 8, and between 8 and 10.










Herbicidal





rate






(
%
)


=




{

(

Fresh





weight





of





shoots





in





a





non


-


treated





plot

)

}

-

{

(

Fresh





weight





of





shoots





in





a





treated





plot

)

}



(

Fresh





weight





of





shoots





in





a





non


-


treated





plot

)


×
100





[

Equation





1

]







Test Example 1
Upland Farming Foliar Treatment Test

A 200-cm2 pot was filled with soil and respective seeds of crabgrass, giant foxtail, velvetleaf, and pigweed were planted in the surface layer thereof, and, after lightly covering with soil, the plants were grown in a greenhouse. When each weed had grown to 5-10 cm in height, a water-dilution of emulsifiable concentrate shown in Formulation Example 2 of each compound under test was applied to foliar parts of weeds by a small atomizer so that the active ingredient would reach a predetermined dose, in an amount equivalent to the application amount of 1000 l/ha. The plants were grown in a greenhouse and 2 weeks after the treatment, herbicidal effects on weeds were examined following the examination criteria.


Results showed that compounds listed below had a herbicidal index of 8 or more with any of the weeds of crabgrass, giant foxtail, velvetleaf, and pigweed at 1000 g/ha. Note that compound numbers correspond to those in Table 3.


Tested Compounds

1-411, 413, 415-418, 420, 422, 431, 433-447, 449-451


Compounds with a Herbicidal Index of 8 or More


1-18, 20-36, 38-59, 61-143, 145-154, 156-160, 163-173, 175, 176, 178-187, 190-198, 200-202, 207, 208, 211-214, 216-221, 224-226, 233, 237-243, 245, 247-251, 253, 256, 258-282, 284-289, 292, 295-303, 305-320, 322-324, 326, 329-342, 344-357, 360-380, 382, 384, 386-389, 393-399, 401-408, 410-411, 413, 415-418, 420, 422-427, 429, 433-447, 449-451.


Test Example 2
Upland Farming Soil Treatment Test

A plastic pot with an area of 70 cm2 was filled with field soil and seeds of crabgrass, giant foxtail, velvetleaf, and pigweed were planted thereto and covered with 0.5 cm of soil. A water-dilution of emulsifiable concentrate shown in Formulation Example 2 was applied to the soil surface uniformly so that the active ingredient would reach a predetermined dose. The plants were grown in a greenhouse and 3 weeks after the treatment, herbicidal effects on weeds were examined following the examination criteria.


Results showed that compounds listed below had a herbicidal index of 8 or more with any of the weeds of crabgrass, giant foxtail, velvetleaf, and pigweed at 1000 g/ha. Note that compound numbers correspond to those in Table 3.


Tested Compounds

1-397, 399-411, 416-418, 420, 422-431, 433-435, 437-447, 449-451.


Compounds with a Herbicidal Index of 8 or More


1-17, 19-49, 51-56, 58-142, 145-160, 162-173, 178, 181-185, 189-191, 193, 194, 196-198, 200, 201, 211-214, 217, 218, 220, 221, 224-226, 230, 233, 237-245, 247-252, 254, 258-295, 297-313, 315-317, 319-324, 326, 329-342, 344-357, 360-380, 382, 383-384, 386-390, 392-397, 399-411, 416-418, 420, 422-429, 431, 433-435, 437-441, 443-445, 447, 449-451.


INDUSTRIAL APPLICABILITY

According to the present invention, novel amidine compounds which are highly safe and may be used as active ingredients in herbicides that are reliably effective at a lesser dose, and herbicides containing these compounds as active ingredients are provided.

Claims
  • 1. A herbicide comprising at least one kind of amidine compound represented by a formula (1)
  • 2. The herbicide according to claim 1, wherein the formula (2) in the formula (1) is a nitrogen-containing heterocyclic group which is 3 to 8-membered, which is saturated or unsaturated, and which is optionally substituted.
  • 3. The herbicide according to claim 1 or 2, wherein the formula (2) in the formula (1) is an optionally-substituted azetidine-1-yl group or an optionally-substituted pyrrolidine-1-yl group.
  • 4. The herbicide according to any one of claims 1 to 3, wherein in the formula (1), A is an optionally-substituted aromatic hydrocarbon group.
  • 5. The herbicide according to any one of claims 1 to 4, wherein in the formula (1), A is a group represented by a formula (4)
  • 6. Amidine compounds represented by a formula (1′)
  • 7. The amidine compounds according to claim 6 or salts thereof, wherein in the formula (1′), G′ is a nitrogen-containing heterocyclic group which is 3 to 8-membered, which is saturated or unsaturated, and which is optionally substituted.
  • 8. The amidine compounds according to claim 6 or salts thereof, wherein in the formula (1′), G′ is an optionally substituted azetidine-1-yl group or an optionally substituted pyrrolidine-1-yl group.
Priority Claims (2)
Number Date Country Kind
2005 224452 Aug 2005 JP national
2006 128341 May 2006 JP national
PCT Information
Filing Document Filing Date Country Kind 371c Date
PCT/JP2006/315337 8/2/2006 WO 00 1/31/2008