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CN113754636B - Quinazoline-containing aza-ether compounds - Google Patents

Quinazoline-containing aza-ether compounds Download PDF

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CN113754636B
CN113754636B CN202010489693.0A CN202010489693A CN113754636B CN 113754636 B CN113754636 B CN 113754636B CN 202010489693 A CN202010489693 A CN 202010489693A CN 113754636 B CN113754636 B CN 113754636B
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amine
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quinazolin
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CN113754636A (en
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刘民华
柳爱平
李立中
成淑芬
张萍
吴明峰
龙楚云
任叶果
刘兴平
王惠峰
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Hunan Research Institute of Chemical Industry
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Abstract

The invention discloses a quinazoline-containing aza ether compound shown in formula (I), an isomer or a salt thereof, and a preparation method and application thereof.
Figure DDA0002520585650000011
Wherein R, R in formula 1 、R 2 M, A and X have the definitions given in the specification. The compound of formula (I) has insecticidal/acaricidal or fungicidal biological activity, and especially has high activity on pests and germs.

Description

Quinazoline-containing aza-ether compounds
Technical Field
The invention belongs to the field of insecticidal/acaricidal and bactericidal agents, and particularly relates to quinazoline-containing aza-ether compounds with insecticidal/acaricidal and bactericidal biological activities, a preparation method thereof, insecticidal/acaricidal and bactericidal agent compositions containing the compounds, and application and a method for controlling pests, acarids and harmful bacteria by using the compounds.
Background
CN109776427a discloses the following structural formulas of quinazoline-containing pyridylether hydrochloride or oxalate S1, S2 and S3, without disclosing their structural characteristics and biological activity. Based on the investigation, the non-salt compounds D1, D2 and D3 thereof were not found. US 20060019975 A1 and WO 2006070284 A1 report azaether compounds D4 and D5, respectively, where the bridge between the quinazoline and the pyridine is a piperidine and pyrrole heterocycle.
Figure GDA0003773939960000011
On-line Scifinder searches also found compounds D6, D7, D8 and D9 based on piperidine and pyrrole heterocycles as the chain bridge between quinazoline and pyridine, but no specific reference is made.
Figure GDA0003773939960000012
In order to obtain novel active molecules, the inventor carries out intensive research on the quinazoline-containing azaether compounds, and finds that the quinazoline-containing azaether compounds are more favorable for chain bridges or nitrogen heterocycles of the compounds with insecticidal/acaricidal and/or bactericidal activities than D1-D9, and the novel quinazoline-containing azaether compounds have broader-spectrum and higher-efficient biological activities than D1-D9.
Disclosure of Invention
The invention provides quinazoline-containing aza-ether compounds with biological activity of preventing and controlling pests/mites, harmful bacteria and the like, which are shown in a formula (I), isomers thereof or salts of the compounds shown in the formula (I):
Figure GDA0003773939960000013
wherein:
I.R are the same or different and are selected from the group consisting of hydrogen, nitro, cyano, halogen, C 1 -C 12 Alkyl radical, C 1 -C 12 Alkoxy radical, C 1 -C 12 Alkylthio radical, C 2 -C 12 Alkenyl radical, C 2 -C 12 Alkynyl, C 3 -C 12 Cycloalkyl or C 3 -C 12 A heterocyclic group; v is selected from N or CR;
II.R 1 、R 2 are identical or different and are selected from the group consisting of hydrogen, nitro, cyano, halogen, C 1 -C 12 Alkyl radical, C 1 -C 12 Alkoxy radical, C 1 -C 12 Alkylthio radical, C 2 -C 12 Alkenyl radical, C 2 -C 12 Alkynyl, C 3 -C 12 Cycloalkyl or C 3 -C 12 A heterocyclic group;
m is selected from an integer from 1 to 4, R is when m is greater than 1 1 May be the same or different;
a is selected from A1, A2, A3, A4, A5, A6, A7 or A8, RS represents that chiral carbon is R/S configuration with any proportion, S represents that chiral carbon is S configuration, and R represents that chiral carbon is R configuration;
Figure GDA0003773939960000021
V.X is selected from O, S, SO or SO 2 ；
In I or II, the hydrogen atoms in the alkyl, alkenyl, alkynyl, cycloalkyl or heterocyclyl group may be partially or fully substituted by the same or different substituents selected from the group consisting of: halogen, nitro, cyano, amino, hydroxy, C 1 -C 6 Alkyl radical, C 1 -C 6 Alkoxy radical, C 1 -C 6 Alkylthio or C 1 -C 6 An alkylamino group;
in the definitions of the compounds (I) given above, the terms used, whether used alone or in compound words, represent the following substituents:
halogen: fluorine, chlorine, bromine and iodine;
alkyl groups: refers to straight or branched chain alkyl;
an alkenyl group; refers to a straight or branched chain alkyl group, and a double bond may be present at any position;
an alkynyl group; refers to a straight or branched chain alkyl group, and may have a triple bond at any position;
halogenation: refers to a compound in which hydrogen atoms are partially or totally substituted by halogen atoms;
cycloalkyl: refers to a saturated or unsaturated cycloalkyl group;
heterocycloalkyl group: saturated or unsaturated heterocycloalkyl, wherein at least 1 is N, O or S;
a salt of a compound of formula (I): refers to salts of compounds of formula (I) with organic or inorganic acids; the organic acid means a carboxylic acid or a sulfonic acid such as acetic acid, trifluoroacetic acid, chloroacetic acid, propionic acid, butyric acid, cyclopentanoic acid, oxalic acid, adipic acid, lauric acid, citric acid, maleic acid, fumaric acid, benzoic acid, methylbenzoic acid, phthalic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, or the like; inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, or the like.
Preferred compounds of the invention are compounds of formula (I) and isomers thereof or salts of compounds of formula (I) wherein:
I.R are the same or different and are selected from the group consisting of hydrogen, nitro, cyano, halogen, C 1 -C 12 Alkyl or halo C 1 -C 12 An alkyl group; v is selected from N or CR;
II.R 1 、R 2 are the same or different and are selected from hydrogen, halogen, C 1 -C 12 Alkyl or halo C 1 -C 12 An alkyl group;
m is selected from an integer from 1 to 4, R is when m is greater than 1 1 May be the same or different;
a is selected from A1, A2, A3, A4, A5, A6, A7 or A8, RS represents that chiral carbon is R/S configuration with any proportion, S represents that chiral carbon is S configuration, and R represents that chiral carbon is R configuration;
Figure GDA0003773939960000031
V.X is selected from O.
The more preferred compounds of formula (I) of the invention are of the formula I-A-D, I-A-E, I-A-F, I-A-G, I-A-H, I-A-I, I-A-J, I-A-K, I-A-L, I-A-M, I-A-N, I-A-O, I-A-P, I-A-Q, I-A-R or I-A-S,
Figure GDA0003773939960000032
wherein:
I.R 1 、R 2 are identical or different and are selected from the group consisting of hydrogen, halogen, C 1 -C 3 Alkyl or halo C 1 -C 3 An alkyl group;
m is selected from an integer from 1 to 4, R is greater than 1 1 May be the same or different;
a is selected from A1, A2, A3, A4, A5, A6, A7 or A8, RS represents that chiral carbon is R/S in any ratio configuration, S represents that chiral carbon is S configuration, and R represents that chiral carbon is R configuration;
Figure GDA0003773939960000033
or IS formed by mixing the raw materials with hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, sorbic acid, malic acid, tartaric acid or citric acid to form IS-A-D, IS-A-E, IS-A-F, IS-A-G, IS-A-H, IS-A-I, IS-A-J, IS-A-K, IS-A-L, IS-A-M, IS-A-N, IS-A-O, IS-A-989898989819 zxft 3543-A-24 zxft 3524-A-4924-A-R or IS-A-S,
Figure GDA0003773939960000034
Figure GDA0003773939960000041
a further preferred compound of formula (I) according to the invention is of formula I-A1-D, I-A1-E, I-A1-F, I-A1-G, I-A1-H, I-A1-I, I-A1-J, I-A1-K, I-A1-L, I-A1-M, I-A1-N, I-A1-O, I-A1-P, I-A1-Q, I-A1-R, I-A1-S, I-A2-D, I-A2-5325 zxft 3425-A2-6235 zxft 3535-A1-3584 zxft 3256-A2-3456 zxft 3256-A2-3232 zxft 3256-A1-3425 zxft 3456-A2-K, I-A2-L, I-A2-M, I-A2-N, I-A2-O, I-A2-P, I-A2-Q, I-A2-R, I-A2-S, I-A3-D, I-A3-E, I-A3-F, I-A3-3925 zxft 3826 3925-A3-H, I-A3-I, I-A3-J, I-A3-K, I-A3-L, I-A3-M, I-A3-N, I-A3-O, I-A3-P, I-A3-Q, I-A3-92 zxft 3592-A3-S, I-A4-D, I-A4- -A4- -A4- -A4- -A4- -A4- -A4- -A4- -A5- -A5- -A5- -A5- -A5- -A5- -A5- -A5- -A5- -A5- -A5- -A4A 5- -A5- -A5- -A5- -A5- -A6- -A6- -A6- -A6- -A6- -A6- -A6- -A6- -A6- -A7- -A7- -A7- -A7- -A7- -H, I-A7-I, I-A7-J, I-A7-K, I-A7-L, I-A7-M, I-A7-N, I-A7-O, I-A7-P, I-A7-Q, I-A7-R, I-A7-S, I-A8-D, I-A8-E, I-A8-9696 zxft 96-A8-3235 zxft 35-A8-H, I-A8-3426 zxft 5626-A8-zxft 3474-A8-K, I-A8-3592-A8-358 zxft 6258-428-A5-428 zxft 428-A-428 zxft-A-4258 zxft 428-A-348 zxft 428-A-428,
Figure GDA0003773939960000051
Figure GDA0003773939960000061
Figure GDA0003773939960000071
Figure GDA0003773939960000081
wherein: r 1 And R 2 Is the same or different and is selected from the group consisting of hydrogen, fluorine, chlorine, bromine, iodine, nitro, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, fluoromethyl, chloromethyl, bromomethyl, iodomethyl, dichloromethyl, difluoromethyl, dibromomethyl, diiodomethyl, trichloromethyl, trifluoromethyl, tribromomethyl, triiodomethyl, 1-fluoroethyl, 1-chloroethyl, 1-bromoethyl, 2-trifluoroethyl, 1-fluoroisopropyl, 1-chloroisopropyl1-bromoisopropyl, methoxymethyl, methoxyethyl, ethoxymethyl, cyclopropyl, cyclopentyl, cyclohexyl, 2-oxocyclopentyl, 3-oxocyclopentyl, 2-allyl, 2-propargyl, 3-chloro-2-allyl, 3,3-dichloro-2-allyl, 3,3-difluoro-2-allyl, heptafluoroisopropyl or 1-methoxyhexafluoroisopropyl, methoxy, trifluoromethoxy, methylthio, trifluoromethylthio, ethoxy, 2-trifluoroethoxy or 2-difluoroethoxy;
or with hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, trifluoromethanesulfonic acid benzene sulfonic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, sorbic acid, malic acid tartrate or citrate IS salt IS-A1-D, IS-A1-E, IS-A1-F, IS-A1-G, IS-A1-H, IS-A1-I, IS-A1-J, IS-A1-K, IS-A1-L, IS-A1-M, IS-A1-N, IS-A1-O, IS-A1-P, IS-A1-Q, IS-A1-R, IS-A1-S, IS-A2-D, IS-A2-7945 zxft 3245-A2-3272 zxft 3754-A3424 zxft 3772-A3424 zxft 3742-A1-8583 zxft 4984H, IS-A2-I, IS-A2-J, IS-A2-K, IS-A2-L, IS-A2-M, IS-A2-N, IS-A2-O, IS-A2-P, IS-A2-Q, IS-A2-R, IS-A2-S, IS-A3-D, IS-A3-E, IS-A3-F, IS-A3-3757 zxft 57-A3-58zxft 5852-A3-3575 zxft 3428-A3-3625 zxft 3826-A3-3526 zxft 3528-A3-3 zxft 3725 zxft 3528-A3-3 zxft 35xft 35ft 3557 zxft 57, IS-A3- -A3- -A3- -A3- -A3- -A4- -A4- -A4- -A4- -A4- -A4- -A4- -A4- -A4- -A4- -A4- -A4- -A4- -A4- -A4- -A5- -A5- -A5- -A4- -A4- -A4- -A4- -A5- -A4A 5- -A5- -A5- -A5- -A5- -A5- -A5- -A5- -A6- -A6- -A6- -A6- -A6- -A6- -A6- -A6- -A6- -A6- -A6- -A6- -A6- -A6- -A6- -R, IS-A6-S, IS-A7-D, IS-A7-E, IS-A7-F, IS-A7-G, IS-A7-H, IS-A7-I, IS-A7-I, IS-A7-I, IS-A7-I, IS-A7-I, IS-A7-I, IS A7-I, IS-A8-I, IS-A8-I, IS-A8-I, IS-A8-I, IS-A8-I, IS-A8-I, IS-A8-I, IS-A8-I, IS-A8-I, IS-A8-I, IS-A8-I, IS-A8-I, IS-A8-I, IS-A8-I, IS-A8-6258 or IS-A8-S.
Particularly preferred compounds of the formula (I) according to the invention are the compounds shown in Table 1 or their salts with hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, sorbic acid, malic acid, tartaric acid or citric acid.
TABLE 1 Compounds of formula (I) which are particularly preferred according to the invention
Figure GDA0003773939960000091
Figure GDA0003773939960000101
Table 2, table 3 and Table 4 show R, R in formula (I) 1 Or R 2 、R m 1 The moiety (c) is not limited to these substituents. Table 5 lists some specific acids of the Acid in formula (IS), but the Acid IS not limited to these acids.
TABLE 2 specific substituents for moieties from which R is selected in the general formula (I)
Figure GDA0003773939960000102
TABLE 3 general formula (I) R 1 Or R 2 Is selected from the group consisting of
Figure GDA0003773939960000103
Figure GDA0003773939960000111
TABLE 4 general formula (I) R m 1 Selected from the group consisting of the moiety-specific substituents
No. R m 1 No. R m 1 No. R m 1 No. R m 1
4-1 H 4-2 6-Cl-7-CH 3 4-3 6-F-7-CH 3 4-4 5-CH 3 -6-Cl
4-5 5-F 4-6 6-F 4-7 7-F 4-8 8-F
4-9 5-Cl 4-10 6-Cl 4-11 7-Cl 4-12 8-Cl
4-13 5-Br 4-14 6-Br 4-15 7-Br 4-16 8-Br
4-17 5-I 4-18 6-I 4-19 7-I 4-20 8-I
4-21 5-CH 3 4-22 6-CH 3 4-23 7-CH 3 4-24 8-CH 3
4-25 5-CH 2 CH 3 4-26 6-CH 2 CH 3 4-27 7-CH 2 CH 3 4-28 8-CH 2 CH 3
4-29 5-CF 3 4-30 6-CF 3 4-31 7-CF 3 4-32 8-CF 3
4-33 6,7-F 2 4-34 6,7-Cl 2 4-35 6,7-Br 2 4-36 6,7-I 2
4-37 6,7-(CH 3 ) 2 4-38 6,7-(OCH 3 ) 2 4-39 6,7-(CH 2 CH 3 ) 2 4-40 6,7-(OCH 2 CH 3 ) 2
4-41 6-F-7-Cl 4-42 6-Cl-7-F 4-43 6-F-7-Br 4-44 6-Cl-7-Br
4-45 6-Br-7-Cl 4-46 6-Br-7-F 4-47 5,6,7-F 3 4-48 5,6,7-Cl 3
4-49 5-CF(CF 3 ) 2 4-50 6-CF(CF 3 ) 2 4-51 7-CF(CF 3 ) 2 4-52 8-CF(CF 3 ) 2
4-53 5-COCH 3 (CF 3 ) 2 4-54 6-COCH 3 (CF 3 ) 2 4-55 7-COCH 3 (CF 3 ) 2 4-56 8-COCH 3 (CF 3 ) 2
4-57 5,6,7,8-F 4 4-58 5,6,7,8-Cl 4 4-59 6-CH 3 -7-Cl 4-60 6-CH 3 -7-F
TABLE 5 partial acids selected from the acids of the general formula (IS)
No. Acid No. Acid No. Acid No. Acid
5-1 Hydrochloric acid 5-2 Sulfuric acid 5-3 Phosphoric acid 5-4 Nitric acid
5-5 Carbonic acid 5-6 Formic acid 5-7 Acetic acid 5-8 Trifluoroacetic acid
5-9 Propionic acid 5-10 Butyric acid 5-11 Cyclopentanoic acid 5-12 Oxalic acid
5-13 Adipic acid 5-14 Benzoic acid 5-15 Para methyl benzoic acid 5-16 Phthalic acid
5-17 Methanesulfonic acid 5-18 Trifluoromethanesulfonic acid 5-19 Benzene sulfonic acid 5-20 P-toluenesulfonic acid
5-21 Dodecyl benzene sulfonic acid 5-22 Lauric acid 5-23 Maleic acid 5-24 Fumaric acid
5-25 Sorbic acid 5-26 Malic acid 5-27 Citric acid 5-28 Tartaric acid
The compounds of the present invention can be illustrated by the specific compounds listed in the compound No. (I-A), but are not intended to limit the present invention. The salts of the compounds of the present invention can be illustrated by the salts of the specific compounds listed in Compound No. (IS-A), but do not limit the present invention.
When R is 2 ＝H，R 1 m The substituents are shown in Table 4 below, the number of the compounds represented by the formula (I) is sequentially I-A1-D1-1-I-A1-D1-60, I-A1-E1-1-I-A1-E1-60, I-A1-F1-1-I-A1-F1-60, I-A1-G1-1-I-A1-G1-60, I-A1-H1-1-I-A1-H1-60, I-A1-I1-1-I-A1-I1-60, I-A1-J1-60, I-A1-K1-1-I-A1-K1-60, I-A1-L1-60, I-A1-L1-60I-A1-M1-1-I-A1-M1-60, I-A1-N1-1-I-A1-N1-60, I-A1-O1-1-I-A1-O1-60, I-A1-P1-1-I-A1-P1-60, I-A1-Q1-1-I-A1-Q1-60, I-A1-R1-1-I-A1-R1-60, I-A1-S1-1-I-A1-S1-60, I-A2-D1-1-I-A2-D1-60, I-A2-E1-1-I-A2-E1-60, I-A2-F1-1-I-A2-F1-60, I-A2-G1-1-I-A2-G1-60, I-A2-H1-1-I-A2-H1-60, I-A2-I1-1-I-A2-I1-60, I-A2-J1-1-I-A2-J1-60, I-A2-K1-1-I-A2-K1-60, I-A2-L1-1-I-A2-L1-60, I-A2-M1-1-I-A2-M1-60, I-A2-N1-1-I-A2-N1-60, I-A2-O1-1-I-A2-O1-60I-A2-P1-1-I-A2-P1-60, I-A2-Q1-1-I-A2-Q1-60, I-A2-R1-1-I-A2-R1-60, I-A2-S1-1-I-A2-S1-60, I-A3-D1-1-I-A3-D1-60, I-A3-E1-1-I-A3-E1-60, I-A3-F1-1-I-A3-F1-60, I-A3-G1-1-I-A3-G1-60, I-A3-H1-1-I-A3-H1-60, I-A3-I1-1-I-A3-I1-60, I-A3-J1-1-I-A3-J1-60, I-A3-K1-1-I-A3-K1-60, I-A3-L1-1-I-A3-L1-60, I-A3-M1-1-I-A3-M1-60I-A3-N1-1-I-A3-N1-60, I-A3-O1-1-I-A3-O1-60, I-A3-P1-1-I-A3-P1-60, I-A3-Q1-1-I-A3-Q1-60, I-A3-R1-1-I-A3-R1-60I-A3-S1-1-I-A3-S1-60, I-A4-D1-1-I-A4-D1-60, I-A4-E1-1-I-A4-E1-60, I-A4-F1-1-I-A4-F1-60, I-A4-G1-1-I-A4-G1-60, I-A4-H1-1-I-A4-H1-60, I-A4-I1-60, I-A4-J1-1-I-A4-J1-60, I-A4-K1-1-I-A4-K1-60, I-A4-L1-1-I-A4-L1-60, I-A4-M1-1-I-A4-M1-60, I-A4-N1-1-I-A4-N1-60, I-A4-O1-1-I-A4-O1-60, I-A4-P1-1-I-A4-P1-60, I-A4-Q1-1-I-A4-Q1-60, I-A4-R1-1-I-A4-R1-60, I-A4-S1-1-I-A4-S1-60, I-A5-D1-1-I-A5-D1-60I-A5-E1-1-I-A5-E1-60, I-A5-F1-1-I-A5-F1-60, I-A5-G1-1-I-A5-G1-60, I-A5-H1-1-I-A5-H1-60, I-A5-I1-60, I-A5-J1-60, I-A5-K1-60, I-A5-L1-60, I-A5-M1-1-I-A5-L1-605-M1-60, I-A5-N1-1-I-A5-N1-60, I-A5-O1-1-I-A5-O1-60, I-A5-P1-1-I-A5-P1-60, I-A5-Q1-1-I-A5-Q1-60I-A5-R1-1-I-A5-R1-60, I-A5-S1-1-I-A5-S1-60, I-A6-D1-1-I-A6-D1-60, I-A6-E1-1-I-A6-E1-60, I-A6-F1-1-I-A6-F1-60I-A6-G1-1-I-A6-G1-60, I-A6-H1-1-I-A6-H1-60, I-A6-I1-1-I-A6-I1-60, I-A6-J1-60, I-A6-K1-60, I-A6-L1-1-I-A6-L1-60, I-A6-M1-60, I-A6-N1-1-I-A6-N1-60, I-A6-O1-1-I-A6-O1-60, I-A6-P1-1-I-A6-P1-60, I-A6-Q1-1-I-A6-Q1-60, I-A6-R1-1-I-A6-R1-60, I-A6-S1-1-I-A6-S1-60, I-A7-D1-1-I-A7-D1-60, I-A7-E1-1-I-A7-E1-60, I-A7-F1-1-I-A7-F1-60, I-A7-G1-1-I-A7-G1-60, I-A7-H1-1-I-A7-H1-60, I-A7-I1-60, I-A7-I1-60I-A7-J1-1-I-A7-J1-60, I-A7-K1-1-I-A7-K1-60, I-A7-L1-60, I-A7-M1-60, I-A7-N1-1-I-A7-N1-60, I-A7-O1-1-I-A7-O1-60, I-A7-P1-60, I-A7-Q1-60, I-A7-R1-1-I-A7-R1-60, I-A7-S1-1-I-A7-S1-60, I-A8-D1-1-I-A8-D1-60, I-A8-E1-1-I-A8-E1-60, I-A8-F1-1-I-A8-F1-60, I-A8-G1-1-I-A8-G1-60, I-A8-H1-1-I-A8-H1-60, I-A8-I1-60, I-A8-J1-1-I-A8-J1-60, I-A8-K1-1-I-A8-K1-60, I-A8-K1-60I-A8-L1-1-I-A8-L1-60, I-A8-M1-1-I-A8-M1-60, I-A8-N1-1-I-A8-N1-60, I-A8-O1-1-I-A8-O1-60, I-A8-P1-1-I-A8-P1-60, I-A8-Q1-1-I-A8-Q1-60, I-A8-R1-1-I-A8-R1-60, or I-A8-S1-1-I-A8-S1-60;
when R is 2 ＝CH 3 ，R 1 m The substituents are shown in Table 4 below, the number of the compounds represented by the formula (I) is sequentially I-A1-D2-1-I-A1-D2-60, I-A1-E2-1-I-A1-E2-60, I-A1-F2-1-I-A1-F2-60, I-A1-G2-1-I-A1-G2-60, I-A1-H2-1-I-A1-H2-60, I-A1-I2-1-I-A1-I2-60, I-A1-J2-1-I-A1-J2-60, I-A1-K2-1-I-A1-K2-60, I-A1-L2-1-I-A1-L2-60, I-A1-L2-60I-A1-M2-1-I-A1-M2-60, I-A1-N2-1-I-A1-N2-60, I-A1-O2-1-I-A1-O2-60, I-A1-P2-1-I-A1-P2-60, I-A1-Q2-1-I-A1-Q2-60, I-A1-R2-1-I-A1-R2-60, I-A1-S2-1-I-A1-S2-60, I-A2-D2-1-I-A2-D2-60, I-A2-E2-1-I-A2-E2-60, I-A2-F2-1-I-A2-F2-60, I-A2-G2-1-I-A2-G2-60, I-A2-H2-1-I-A2-H2-60, I-A2-I2-1-I-A2-I2-60、I-A2-J2-1－I-A2-J2-60、I-A2-K2-1－I-A2-K2-60、I-A2-L2-1－I-A2-L2-60、I-A2-M2-1－I-A2-M2-60、I-A2-N2-1－I-A2-N2-60、I-A2-O2-1－I-A2-O2-60、I-A2-P2-1－I-A2-P2-60、I-A2-Q2-1－I-A2-Q2-60、I-A2-R2-1－I-A2-R2-60、I-A2-S2-1－I-A2-S2-60、I-A3-D2-1－I-A3-D2-60、I-A3-E2-1－I-A3-E2-60、I-A3-F2-1－I-A3-F2-60、I-A3-G2-1－I-A3-G2-60、I-A3-H2-1－I-A3-H2-60、I-A3-I2-1－I-A3-I2-60、I-A3-J2-1－I-A3-J2-60、I-A3-K2-1－I-A3-K2-60、I-A3-L2-1－I-A3-L2-60、I-A3-M2-1－I-A3-M2-60、I-A3-N2-1－I-A3-N2-60、I-A3-O2-1－I-A3-O2-60、I-A3-P2-1－I-A3-P2-60、I-A3-Q2-1－I-A3-Q2-60、I-A3-R2-1－I-A3-R2-60、I-A3-S2-1－I-A3-S2-60、I-A4-D2-1－I-A4-D2-60、I-A4-E2-1－I-A4-E2-60、I-A4-F2-1－I-A4-F2-60、I-A4-G2-1－I-A4-G2-60、I-A4-H2-1－I-A4-H2-60、I-A4-I2-1－I-A4-I2-60、I-A4-J2-1－I-A4-J2-60、I-A4-K2-1－I-A4-K2-60、I-A4-L2-1－I-A4-L2-60、I-A4-M2-1－I-A4-M2-60、I-A4-N2-1－I-A4-N2-60、I-A4-O2-1－I-A4-O2-60、I-A4-P2-1－I-A4-P2-60、I-A4-Q2-1－I-A4-Q2-60、I-A4-R2-1－I-A4-R2-60、I-A4-S2-1－I-A4-S2-60、I-A5-D2-1－I-A5-D2-60、I-A5-E2-1－I-A5-E2-60、I-A5-F2-1－I-A5-F2-60、I-A5-G2-1－I-A5-G2-60、I-A5-H2-1－I-A5-H2-60、I-A5-I2-1－I-A5-I2-60、I-A5-J2-1－I-A5-J2-60、I-A5-K2-1－I-A5-K2-60、I-A5-L2-1－I-A5-L2-60、I-A5-M2-1－I-A5-M2-60、I-A5-N2-1－I-A5-N2-60、I-A5-O2-1－I-A5-O2-60、I-A5-P2-1－I-A5-P2-60、I-A5-Q2-1－I-A5-Q2-60、I-A5-R2-1－I-A5-R2-60、I-A5-S2-1－I-A5-S2-60、I-A6-D2-1－I-A6-D2-60、I-A6-E2-1－I-A6-E2-60、I-A6-F2-1－I-A6-F2-60、I-A6-G2-1－I-A6-G2-60、I-A6-H2-1－I-A6-H2-60、I-A6-I2-1－I-A6-I2-60、I-A6-J2-1－I-A6-J2-60、I-A6-K2-1－I-A6-K2-60、I-A6-L2-1－I-A6-L2-60、I-A6-M2-1－I-A6-M2-60、I-A6-N2-1－I-A6-N2-60、I-A6-O2-1－I-A6-O2-60、I-A6-P2-1－I-A6-P2-60、I-A6-Q2-1－I-A6-Q2-60、I-A6-R2-1－I-A6-R2-60、I-A6-S2-1－I-A6-S2-60、I-A7-D2-1－I-A7-D2-60、I-A7-E2-1－I-A7-E2-60、I-A7-F2-1－I-A7-F2-60、I-A7-G2-1－I-A7-G2-60、I-A7-H2-1－I-A7-H2-60、I-A7-I2-1－I-A7-I2-60、I-A7-J2-1－I-A7-J2-60、I-A7-K2-1－<xnotran> I-A7-K2-60, I-A7-L2-1-I-A7-L2-60, I-A7-M2-1-I-A7-M2-60, I-A7-N2-1-I-A7-N2-60, I-A7-O2-1-I-A7-O2-60, I-A7-P2-1-I-A7-P2-60, I-A7-Q2-1-I-A7-Q2-60, I-A7-R2-1-I-A7-R2-60, I-A7-S2-1-I-A7-S2-60, I-A8-D2-1-I-A8-D2-60, I-A8-E2-1-I-A8-E2-60, I-A8-F2-1-I-A8-F2-60, I-A8-G2-1-I-A8-G2-60, I-A8-H2-1-I-A8-H2-60, I-A8-I2-1-I-A8-I2-60, I-A8-J2-1-I-A8-J2-60, I-A8-K2-1-I-A8-K2-60, I-A8-L2-1-I-A8-L2-60, I-A8-M2-1-I-A8-M2-60, </xnotran> I-A8-N2-1-I-A8-N2-60, I-A8-O2-1-I-A8-O2-60, I-A8-P2-1-I-A8-P2-60, I-A8-Q2-1-I-A8-Q2-60, I-A8-R2-1-I-A8-R2-60 or I-A8-S2-1-I-A8-S2-60;
when R is 2 ＝CH 2 CH 3 ，R 1 m The substituents are shown in Table 4 below, the number of the compounds represented by the formula (I) is sequentially I-A1-D3-1-I-A1-D3-60, I-A1-E3-1-I-A1-E3-60, I-A1-F3-1-I-A1-F3-60, I-A1-G3-1-I-A1-G3-60, I-A1-H3-1-I-A1-H3-60, I-A1-I3-1-I-A1-I3-60, I-A1-J3-1-I-A1-J3-60, I-A1-K3-1-I-A1-K3-60, I-A1-L3-1-I-A1-L3-60, I-A1-L3-60I-A1-M3-1-I-A1-M3-60, I-A1-N3-1-I-A1-N3-60, I-A1-O3-1-I-A1-O3-60, I-A1-P3-1-I-A1-P3-60, I-A1-Q3-1-I-A1-Q3-60, I-A1-R3-1-I-A1-R3-60, I-A1-S3-1-I-A1-S3-60, I-A2-D3-1-I-A2-D3-60, I-A2-E3-1-I-A2-E3-60, I-A2-F3-1-I-A2-F3-60, I-A2-G3-1-I-A2-G3-60, I-A2-H3-1-I-A2-H3-60, I-A2-I3-1-I-A2-I3-60, I-A2-J3-1-I-A2-J3-60, I-A2-K3-1-I-A2-K3-60, I-A2-L3-1-I-A2-L3-60, I-A2-M3-1-I-A2-M3-60, I-A2-N3-1-I-A2-N3-60, I-A2-O3-1-I-A2-O3-60, I-A2-M3-60I-A2-P3-1-I-A2-P3-60, I-A2-Q3-1-I-A2-Q3-60, I-A2-R3-1-I-A2-R3-60, I-A2-S3-1-I-A2-S3-60, I-A3-D3-1-I-A3-D3-60, I-A3-E3-1-I-A3-E3-60, I-A3-F3-1-I-A3-F3-60, I-A3-G3-1-I-A3-G3-60, I-A3-H3-1-I-A3-H3-60, I-A3-I3-1-I-A3-I3-60, I-A3-J3-1-I-A3-J3-60, I-A3-K3-1-I-A3-K3-60, I-A3-L3-1-I-A3-L3-60, I-A3-M3-1-I-A3-M3-60, I-A3-N3-1-I-A3-N3-60, I-A3-O3-1-I-A3-O3-60, I-A3-O3-60I-A3-P3-1-I-A3-P3-60, I-A3-Q3-1-I-A3-Q3-60, I-A3-R3-1-I-A3-R3-60, I-A3-S3-1-I-A3-S3-60, I-A4-D3-1-I-A4-D3-60, I-A4-E3-1-I-A4-E3-60, I-A4-F3-1-I-A4-F3-60-60, I-A4-G3-1-I-A4-G3-60, I-A4-H3-1-I-A4-H3-60, I-A4-I3-1-I-A4-I3-60, I-A4-J3-1-I-A4-J3-60, I-A4-K3-1-I-A4-K3-60, I-A4-L3-1-I-A4-L3-60, I-A4-M3-1-I-A4-M3-60, I-A4-N3-1-I-A4-N3-60, I-A4-O3-1-I-A4-O3-60I-A4-P3-1-I-A4-P3-60, I-A4-Q3-1-I-A4-Q3-60, I-A4-R3-1-I-A4-R3-60, I-A4-S3-1-I-A4-S3-60, I-A5-D3-1-I-A5-D3-60, I-A5-E3-1-I-A5-E3-60, I-A5-F3-1-I-A5-F3-60, I-A5-G3-1-I-A5-G3-60, I-A5-H3-1-I-A5-H3-60, I-A5-I3-1-I-A5-I3-60, I-A5-I3-60, I-A5-J3-1-I-A5-J3-60, I-A5-K3-1-I-A5-K3-60, I-A5-L3-1-I-A5-L3-60, I-A5-M3-1-I-A5-M3-60, I-A5-N3-1-I-A5-N3-60, I-A5-O3-1-I-A5-O3-60, I-A5-P3-1-I-A5-P3-60, I-A5-Q3-1-I-A5-Q3-60, I-A5-R3-1-I-A5-R3-60, I-A5-S3-1-I-A5-S3-60, I-A5-I-A5-L3-60I-A6-D3-1-I-A6-D3-60, I-A6-E3-1-I-A6-E3-60, I-A6-F3-1-I-A6-F3-60, I-A6-G3-1-I-A6-G3-60, I-A6-H3-1-I-A6-H3-60, I-A6-I3-1-I-A6-I3-60, I-A6-J3-1-I-A6-J3-60, I-A6-K3-1-I-A6-K3-60, I-A6-L3-1-I-A6-L3-60, I-A6-M3-1-I-A6-M3-60, I-A6-N3-1-I-A6-N3-60, I-A6-O3-1-I-A6-O3-60, I-A6-P3-1-I-A6-P3-60, I-A6-Q3-1-I-A6-Q3-60, I-A6-R3-1-I-A6-R3-60, I-A6-S3-1-I-A6-S3-60, I-A7-D3-1-I-A7-D3-60, I-A7-E3-1-I-A7-E3-60, I-A7-F3-1-I-A7-F3-60, I-A6-Q3-60, I-A6-D3-1-I-A7-D3-60, I-A7-E3-1-I-A7-E3-60I-A7-G3-1-I-A7-G3-60, I-A7-H3-1-I-A7-H3-60, I-A7-I3-1-I-A7-I3-60, I-A7-J3-1-I-A7-J3-60, I-A7-K3-1-I-A7-K3-60, I-A7-L3-1-I-A7-L3-60, I-A7-M3-1-I-A7-M3-60, I-A7-N3-1-I-A7-N3-60, I-A7-O3-1-I-A7-O3-60, I-A7-P3-1-I-A7-P3-60, I-A7-Q3-1-I-A7-Q3-60, I-A7-R3-1-I-A7-R3-60, I-A7-S3-1-I-A7-S3-60, I-A8-D3-1-I-A8-D3-60, I-A8-E3-1-I-A8-E3-60, I-A8-F3-1-I-A8-F3-60, I-A8-G3-1-I-A8-G3-60, I-A8-H3-1-I-A8-H3-60, I-A8-I3-1-I-A8-I3-60, I-A8-I3-60I-A8-J3-1-I-A8-J3-60, I-A8-K3-1-I-A8-K3-60, I-A8-L3-1-I-A8-L3-60, I-A8-M3-1-I-A8-M3-60, I-A8-N3-1-I-A8-N3-60, I-A8-O3-1-I-A8-O3-60, I-A8-P3-1-I-A8-P3-60, I-A8-Q3-1-I-A8-Q3-60, I-A8-R3-1-I-A8-R3-60, or I-A8-S3-1-I-A8-S3-60;
when R is 2 ＝F，R 1 m The substituents are shown in Table 4, and the formula (I) is representedThe compounds are numbered as I-A1-D4-1-I-A1-D4-60, I-A1-E4-1-I-A1-E4-60, I-A1-F4-1-I-A1-F4-60, I-A1-G4-1-I-A1-G4-60, I-A1-H4-1-I-A1-H4-60, I-A1-I4-1-I-A1-I4-60, I-A1-J4-1-I-A1-J4-60, I-A1-K4-1-I-A1-K4-60, I-A1-L4-1-I-A1-L4-60 in sequence I-A1-M4-1-I-A1-M4-60, I-A1-N4-1-I-A1-N4-60, I-A1-O4-1-I-A1-O4-60, I-A1-P4-1-I-A1-P4-60, I-A1-Q4-1-I-A1-Q4-60, I-A1-R4-1-I-A1-R4-60, I-A1-S4-1-I-A1-S4-60, I-A2-D4-1-I-A2-D4-60, I-A2-E4-1-I-A2-E4-60, I-A2-F4-1-I-A2-F4-60, I-A1-Q4-60, I-A1-R4-60, I-A2-D4-60, I-A2-A4-F4-60, I-A2-G4-1-I-A2-G4-60, I-A2-H4-1-I-A2-H4-60, I-A2-I4-1-I-A2-I4-60, I-A2-J4-1-I-A2-J4-60, I-A2-K4-1-I-A2-K4-60, I-A2-L4-1-I-A2-L4-60, I-A2-M4-1-I-A2-M4-60, I-A2-N4-1-I-A2-N4-60, I-A2-O4-1-I-A2-O4-60, I-A2-P4-1-I-A2-P4-60I-A2-Q4-1-I-A2-Q4-60, I-A2-R4-1-I-A2-R4-60, I-A2-S4-1-I-A2-S4-60, I-A3-D4-1-I-A3-D4-60, I-A3-E4-1-I-A3-E4-60, I-A3-F4-1-I-A3-F4-60, I-A3-G4-1-I-A3-G4-60, I-A3-H4-1-I-A3-H4-60, I-A3-I4-1-I-A3-I4-60, I-A3-J4-1-I-A3-J4-60, I-A3-K4-1-I-A3-K4-60, I-A3-L4-1-I-A3-L4-60, I-A3-M4-1-I-A3-M4-60, I-A3-N4-1-I-A3-N4-60, I-A3-O4-1-I-A3-O4-60, I-A3-P4-1-I-A3-P4-60, I-A3-Q4-1-I-A3-Q4-60, I-A3-R4-1-I-A3-R4-60, I-A3-S4-1-I-A3-S4-60, I-A3-N-I-A3-N4-60, I-A3-N4-O4-60, I-A3-R4-60, I-A3-S4-P4-60, and S4-C I-A4-D4-1-I-A4-D4-60, I-A4-E4-1-I-A4-E4-60, I-A4-F4-1-I-A4-F4-60, I-A4-G4-1-I-A4-G4-60, I-A4-H4-1-I-A4-H4-60, I-A4-I4-1-I-A4-I4-60, I-A4-J4-1-I-A4-J4-60, I-A4-K4-1-I-A4-K4-60, I-A4-L4-1-I-A4-L4-60, I-A4-M4-1-I-A4-M4-60, I-A4-N4-1-I-A4-N4-60, I-A4-O4-1-I-A4-O4-60, I-A4-P4-1-I-A4-P4-60, I-A4-Q4-1-I-A4-Q4-60I-A4-R4-1-I-A4-R4-60, I-A4-S4-1-I-A4-S4-60, I-A5-D4-1-I-A5-D4-60, I-A5-E4-1-I-A5-E4-60, I-A5-F4-1-I-A5-F4-60I-A5-G4-1-I-A5-G4-60, I-A5-H4-1-I-A5-H4-60, I-A5-I4-1-I-A5-I4-60, I-A5-J4-1-I-A5-J4-60, I-A5-K4-1-I-A5-K4-60, I-A5-L4-1-I-A5-L4-60, I-A5-M4-1-I-A5-M4-60, I-A5-N4-1-I-A5-N4-60, I-A5-O4-1-I-A5-O4-60, I-A5-P4-1-I-A5-P4-60, I-A5-Q4-1-I-A5-Q4-60, I-A5-R4-1-I-A5-R4-60, I-A5-S4-1-I-A5-S4-60, I-A6-D4-1-I-A6-D4-60, I-A6-E4-1-I-A6-E4-60, I-A6-F4-1-I-A6-F4-60, I-A6-G4-1-I-A6-G4-60, I-A6-H4-1-I-A6-H4-60, I-A6-I4-1-I-A6-I4-60, I-A6-J4-1-I-A6-J4-60, I-A6-K4-1-I-A6-K4-60, I-A6-L4-1-I-A6-L4-60, I-A6-M4-1-I-A6-M4-60, I-A6-N4-1-I-A6-N4-60, I-A6-L4-60I-A6-O4-1-I-A6-O4-60, I-A6-P4-1-I-A6-P4-60, I-A6-Q4-1-I-A6-Q4-60, I-A6-R4-1-I-A6-R4-60, I-A6-S4-1-I-A6-S4-60, I-A7-D4-1-I-A7-D4-60, I-A7-E4-1-I-A7-E4-60, I-A7-F4-1-I-A7-F4-60, I-A7-G4-1-I-A7-G4-60, I-A7-H4-1-I-A7-H4-60, I-A7-I4-1-I-A7-I4-60, I-A7-J4-1-I-A7-J4-60, I-A7-K4-1-I-A7-K4-60, I-A7-L4-1-I-A7-L4-60, I-A7-M4-1-I-A7-M4-60, I-A7-N4-1-I-A7-N4-60, I-A7-O4-1-I-A7-O4-60, I-A7-P4-1-I-A7-P4-60, I-A7-Q4-1-I-A7-Q4-60, I-A7-L-C4-C60I-A7-R4-1-I-A7-R4-60, I-A7-S4-1-I-A7-S4-60, I-A8-D4-1-I-A8-D4-60, I-A8-E4-1-I-A8-E4-60, I-A8-F4-1-I-A8-F4-60, I-A8-G4-1-I-A8-G4-60, I-A8-H4-1-I-A8-H4-60, I-A8-I4-1-I-A8-I4-60, I-A8-J4-1-I-A8-J4-60, I-A8-K4-1-I-A8-K4-60, I-A8-L4-1-I-A8-L4-60, I-A8-M4-1-I-A8-M4-60, I-A8-N4-1-I-A8-N4-60, I-A8-O4-1-I-A8-O4-60, I-A8-P4-1-I-A8-P4-60, I-A8-Q4-1-I-A8-Q4-60, I-A8-R4-1-I-A8-R4-60, or I-A8-S4-1-I-A8-S4-60;
when R is 2 ＝Cl，R 1 m The substituents are shown in Table 4 below, the number of the compounds represented by the formula (I) is sequentially I-A1-D5-1-I-A1-D5-60, I-A1-E5-1-I-A1-E5-60, I-A1-F5-1-I-A1-F5-60, I-A1-G5-1-I-A1-G5-60, I-A1-H5-1-I-A1-H5-60, I-A1-I5-1-I-A1-I5-60, I-A1-J5-1-I-A1-J5-60, I-A1-K5-1-I-A1-K5-60, I-A1-L5-1-I-A1-L5-60, I-A1-L5-C1-C5-C1, C5-C1-C5-C I-A1-M5-1-I-A1-M5-60, I-A1-N5-1-I-A1-N5-60, I-A1-O5-1-I-A1-O5-60, I-A1-P5-1-I-A1-P5-60, I-A1-Q5-1-I-A1-Q5-60, I-A1-R5-1-I-A1-R5-60, I-A1-S5-1-I-A1-S5-60, I-A2-D5-1-I-A2-D5-60, I-A2-E5-1-I-A2-E5-60, I-A2-F5-1-I-A2-F5-60, I-A2-G5-1-I-A2-G5-60, I-A2-H5-1-I-A2-H5-60, I-A2-I5-1-I-A2-I5-60, I-A2-J5-1-I-A2-J5-60, I-A2-K5-1-I-A2-K5-60, I-A2-L5-1-I-A2-L5-60, I-A2-M5-1-I-A2-M5-60, I-A2-N5-1-I-A2-N5-60, I-A2-O5-1-I-A2-O5-60, I-A2-P5-1-I-A2-P5-60, I-A2-P5-I-A2-K5-60, I-A2-L5-60, I-A2-L5-60, Q5-Q-5-60I-A2-Q5-60、I-A2-R5-1－I-A2-R5-60、I-A2-S5-1－I-A2-S5-60、I-A3-D5-1－I-A3-D5-60、I-A3-E5-1－I-A3-E5-60、I-A3-F5-1－I-A3-F5-60、I-A3-G5-1－I-A3-G5-60、I-A3-H5-1－I-A3-H5-60、I-A3-I5-1－I-A3-I5-60、I-A3-J5-1－I-A3-J5-60、I-A3-K5-1－I-A3-K5-60、I-A3-L5-1－I-A3-L5-60、I-A3-M5-1－I-A3-M5-60、I-A3-N5-1－I-A3-N5-60、I-A3-O5-1－I-A3-O5-60、I-A3-P5-1－I-A3-P5-60、I-A3-Q5-1－I-A3-Q5-60、I-A3-R5-1－I-A3-R5-60、I-A3-S5-1－I-A3-S5-60、I-A4-D5-1－I-A4-D5-60、I-A4-E5-1－I-A4-E5-60、I-A4-F5-1－I-A4-F5-60、I-A4-G5-1－I-A4-G5-60、I-A4-H5-1－I-A4-H5-60、I-A4-I5-1－I-A4-I5-60、I-A4-J5-1－I-A4-J5-60、I-A4-K5-1－I-A4-K5-60、I-A4-L5-1－I-A4-L5-60、I-A4-M5-1－I-A4-M5-60、I-A4-N5-1－I-A4-N5-60、I-A4-O5-1－I-A4-O5-60、I-A4-P5-1－I-A4-P5-60、I-A4-Q5-1－I-A4-Q5-60、I-A4-R5-1－I-A4-R5-60、I-A4-S5-1－I-A4-S5-60、I-A5-D5-1－I-A5-D5-60、I-A5-E5-1－I-A5-E5-60、I-A5-F5-1－I-A5-F5-60、I-A5-G5-1－I-A5-G5-60、I-A5-H5-1－I-A5-H5-60、I-A5-I5-1－I-A5-I5-60、I-A5-J5-1－I-A5-J5-60、I-A5-K5-1－I-A5-K5-60、I-A5-L5-1－I-A5-L5-60、I-A5-M5-1－I-A5-M5-60、I-A5-N5-1－I-A5-N5-60、I-A5-O5-1－I-A5-O5-60、I-A5-P5-1－I-A5-P5-60、I-A5-Q5-1－I-A5-Q5-60、I-A5-R5-1－I-A5-R5-60、I-A5-S5-1－I-A5-S5-60、I-A6-D5-1－I-A6-D5-60、I-A6-E5-1－I-A6-E5-60、I-A6-F5-1－I-A6-F5-60、I-A6-G5-1－I-A6-G5-60、I-A6-H5-1－I-A6-H5-60、I-A6-I5-1－I-A6-I5-60、I-A6-J5-1－I-A6-J5-60、I-A6-K5-1－I-A6-K5-60、I-A6-L5-1－I-A6-L5-60、I-A6-M5-1－I-A6-M5-60、I-A6-N5-1－I-A6-N5-60、I-A6-O5-1－I-A6-O5-60、I-A6-P5-1－I-A6-P5-60、I-A6-Q5-1－I-A6-Q5-60、I-A6-R5-1－I-A6-R5-60、I-A6-S5-1－I-A6-S5-60、I-A7-D5-1－I-A7-D5-60、I-A7-E5-1－I-A7-E5-60、I-A7-F5-1－I-A7-F5-60、I-A7-G5-1－I-A7-G5-60、I-A7-H5-1－I-A7-H5-60、I-A7-I5-1－I-A7-I5-60、I-A7-J5-1－I-A7-J5-60、I-A7-K5-1－I-A7-K5-60、I-A7-L5-1－I-A7-L5-60、I-A7-M5-1－I-A7-M5-60、I-A7-N5-1－I-A7-N5-60、I-A7-O5-1－I-A7-O5-60、I-A7-P5-1－I-A7-P5-60、I-A7-Q5-1－I-A7-Q5-60、I-A7-R5-1－I-A7-R5-60、I-A7-S5-1－I-A7-S5-60, I-A8-D5-1-I-A8-D5-60, I-A8-E5-1-I-A8-E5-60, I-A8-F5-1-I-A8-F5-60, I-A8-G5-1-I-A8-G5-60, I-A8-H5-1-I-A8-H5-60, I-A8-I5-1-I-A8-I5-60, I-A8-J5-1-I-A8-J5-60, I-A8-K5-1-I-A8-K5-60I-A8-L5-1-I-A8-L5-60, I-A8-M5-1-I-A8-M5-60, I-A8-N5-1-I-A8-N5-60, I-A8-O5-1-I-A8-O5-60, I-A8-P5-1-I-A8-P5-60, I-A8-Q5-1-I-A8-Q5-60, I-A8-R5-1-I-A8-R5-60, or I-A8-S5-1-I-A8-S5-60;
when R is 2 ＝Br，R 1 m The substituents are shown in Table 4 below, the number of the represented compounds of formula (I) is sequentially I-A1-D6-1-I-A1-D6-60, I-A1-E6-1-I-A1-E6-60, I-A1-F6-1-I-A1-F6-60, I-A1-G6-1-I-A1-G6-60, I-A1-H6-1-I-A1-H6-60, I-A1-I6-1-I-A1-I6-60, I-A1-J6-1-I-A1-J6-60, I-A1-K6-1-I-A1-K6-60, I-A1-L6-1-I-A1-L6-60, I-A1-D6-1-L6-60I-A1-M6-1-I-A1-M6-60, I-A1-N6-1-I-A1-N6-60, I-A1-O6-1-I-A1-O6-60, I-A1-P6-1-I-A1-P6-60, I-A1-Q6-1-I-A1-Q6-60, I-A1-R6-1-I-A1-R6-60, I-A1-S6-1-I-A1-S6-60, I-A2-D6-1-I-A2-D6-60, I-A2-E6-1-I-A2-E6-60, I-A2-F6-1-I-A2-F6-60, I-A2-G6-1-I-A2-G6-60, I-A2-H6-1-I-A2-H6-60, I-A2-I6-1-I-A2-I6-60, I-A2-J6-1-I-A2-J6-60, I-A2-K6-1-I-A2-K6-60, I-A2-L6-1-I-A2-L6-60, I-A2-M6-1-I-A2-M6-60, I-A2-N6-1-I-A2-N6-60, I-A2-O6-1-I-A2-O6-60, I-A2-O6-60I-A2-P6-1-I-A2-P6-60, I-A2-Q6-1-I-A2-Q6-60, I-A2-R6-1-I-A2-R6-60, I-A2-S6-1-I-A2-S6-60, I-A3-D6-1-I-A3-D6-60, I-A3-E6-1-I-A3-E6-60, I-A3-F6-1-I-A3-F6-60, I-A3-G6-1-I-A3-G6-60, I-A3-H6-1-I-A3-H6-60, I-A3-I6-1-I-A3-I6-60, I-A3-J6-1-I-A3-J6-60, I-A3-K6-1-I-A3-K6-60, I-A3-L6-1-I-A3-L6-60, I-A3-M6-1-I-A3-M6-60, I-A3-N6-1-I-A3-N6-60, I-A3-O6-1-I-A3-O6-60, I-A3-P6-1-I-A3-P6-60, I-A3-Q6-1-I-A3-Q6-60, I-A3-R6-1-I-A3-R6-60, I-A3-R6-60I-A3-S6-1-I-A3-S6-60, I-A4-D6-1-I-A4-D6-60, I-A4-E6-1-I-A4-E6-60, I-A4-F6-1-I-A4-F6-60, I-A4-G6-1-I-A4-G6-60, I-A4-H6-1-I-A4-H6-60, I-A4-I6-1-I-A4-I6-60, I-A4-J6-1-I-A4-J6-60, I-A4-K6-1-I-A4-K6-60, I-A4-L6-1-I-A4-L6-60, I-A4-M6-1-I-A4-M6-60, I-A4-N6-1-I-A4-N6-60, I-A4-O6-1-I-A4-O6-60. I-A4-P6-1-I-A4-P6-60, I-A4-Q6-1-I-A4-Q6-60, I-A4-R6-1-I-A4-R6-60, I-A4-S6-1-I-A4-S6-60, I-A5-D6-1-I-A5-D6-60, I-A5-E6-1-I-A5-E6-60, I-A5-F6-1-I-A5-F6-60, I-A5-G6-1-I-A5-G6-60, I-A5-H6-1-I-A5-H6-60, I-A5-I6-1-I-A5-I6-60, I-A5-I6-60I-A5-J6-1-I-A5-J6-60, I-A5-K6-1-I-A5-K6-60, I-A5-L6-1-I-A5-L6-60, I-A5-M6-1-I-A5-M6-60, I-A5-N6-1-I-A5-N6-60, I-A5-O6-1-I-A5-O6-60, I-A5-P6-1-I-A5-P6-60, I-A5-Q6-1-I-A5-Q6-60, I-A5-R6-1-I-A5-R6-60, I-A5-S6-1-I-A5-S6-60, I-A6-D6-1-I-A6-D6-60, I-A6-E6-1-I-A6-E6-60, I-A6-F6-1-I-A6-F6-60, I-A6-G6-1-I-A6-G6-60, I-A6-H6-1-I-A6-H6-60, I-A6-I6-1-I-A6-I6-60, I-A6-J6-1-I-A6-J6-60, I-A6-K6-1-I-A6-K6-60, I-A6-L6-1-I-A6-L6-60, I-A6-L6-60I-A6-M6-1-I-A6-M6-60, I-A6-N6-1-I-A6-N6-60, I-A6-O6-1-I-A6-O6-60, I-A6-P6-1-I-A6-P6-60, I-A6-Q6-1-I-A6-Q6-60, I-A6-R6-1-I-A6-R6-60, I-A6-S6-1-I-A6-S6-60, I-A7-D6-1-I-A7-D6-60, I-A7-E6-1-I-A7-E6-60, I-A7-F6-1-I-A7-F6-60, I-A7-G6-1-I-A7-G6-60, I-A7-H6-1-I-A7-H6-60, I-A7-I6-1-I-A7-I6-60, I-A7-J6-1-I-A7-J6-60, I-A7-K6-1-I-A7-K6-60, I-A7-L6-1-I-A7-L6-60, I-A7-M6-1-I-A7-M6-60, I-A7-N6-1-I-A7-N6-60, I-A7-O6-1-I-A7-O6-60, I-A7-M6-60, I-A7-H6-I-A7-K6-60I-A7-P6-1-I-A7-P6-60, I-A7-Q6-1-I-A7-Q6-60, I-A7-R6-1-I-A7-R6-60, I-A7-S6-1-I-A7-S6-60, I-A8-D6-1-I-A8-D6-60, I-A8-E6-1-I-A8-E6-60, I-A8-F6-1-I-A8-F6-60, I-A8-G6-1-I-A8-G6-60, I-A8-H6-1-I-A8-H6-60, I-A8-I6-1-I-A8-I6-60, I-A8-J6-1-I-A8-J6-60, I-A8-K6-1-I-A8-K6-60, I-A8-L6-1-I-A8-L6-60, I-A8-M6-1-I-A8-M6-60, I-A8-N6-1-I-A8-N6-60, I-A8-O6-1-I-A8-O6-60, I-A8-P6-1-I-A8-P6-60, I-A8-Q6-1-I-A8-Q6-60, I-A8-R6-1-I-A8-R6-60, or I-A8-S6-1-I-A8-S6-60;
the compounds of the present invention may exist in the form of one or more isomers. Isomers include enantiomers, diastereomers, geometric isomers and cis-trans isomers. The compounds of formula (I) according to the invention, in which the carbon-carbon double bonds are linked to different substituents, may form geometrical isomers (Z and E represent different configurations, respectively), and the invention includes both the Z and E isomers and mixtures thereof in any proportion. The compound shown in the formula (I) forms stereoisomers (R and S respectively represent different configurations) due to the fact that four different substituents are connected to one carbon atom of the compound, and the compound comprises an R-type isomer, an S-type isomer and a mixture of the R-type isomer and the S-type isomer in any proportion. The invention relates to a compound shown in formula (I), wherein more than 2 substituents are connected on a cycloalkyl or a heterocycloalkyl to form cis-trans isomers (different configurations are respectively represented by cis and trans), and the invention comprises cis isomers and trans isomers and mixtures of the cis isomers and the trans isomers in any proportion.
The invention also relates to a composition for controlling pests, harmful bacteria, comprising a biologically effective amount of a compound of formula (I) and at least one further component selected from the group consisting of surfactants, solid diluents and liquid diluents.
The invention also relates to a composition for controlling pests, harmful bacteria, comprising a biologically effective amount of a compound of formula (I) and an effective amount of at least one further biologically active compound or agent.
The invention also relates to a method for controlling pests, harmful bacteria, which comprises contacting a biologically effective amount of a compound of formula (I) with the pests, harmful bacteria or their environment. Also disclosed is a method for controlling pests or harmful bacteria by contacting the pests or harmful bacteria or their environment with a biologically effective amount of a compound of formula (I) or a mixture comprising a compound of formula (I) and a biologically effective amount of at least one additional compound or agent.
The compounds of formula (I) according to the invention have a broad spectrum of activity: some compounds can be used for preventing and controlling harmful germs and pests; and some compounds have high biological activity to some target harmful germs, so that good effect can be obtained under low dosage.
Preferred compositions of the present invention are those containing the preferred compounds described above. Preferred methods are those using the preferred compounds described above.
The compounds of the present invention may be further illustrated by a portion of the compounds of formula (I) listed in Table 6 belowHowever, the present invention is not limited thereto. The melting points given in the present invention are uncorrected. When the compound of formula (I) of the present invention is a viscous solid, some viscous solids will solidify to form a non-viscous solid after standing; when the compound of formula (I) of the present invention is a viscous liquid, some of the viscous liquid will solidify after standing; the compound of the invention can be observed in LC-MS (APCI) to obtain a molecular ion peak; process for preparing compounds 1 H NMR with TMS as internal standard, CDCl 3 As a solvent.
TABLE 6
Figure GDA0003773939960000191
Figure GDA0003773939960000201
Figure GDA0003773939960000211
Figure GDA0003773939960000221
The salts of the compounds of the present invention are illustrated in Table 7, but are not intended to limit the invention.
Table 7 salts of some of the compounds
Figure GDA0003773939960000222
The compound of formula (I) of the present invention can be obtained by the reaction formula 1 shown below; the (II) in the reaction formula 1 can be obtained by the reaction formula 2 shown below; (IV) in the reaction formula 2 can be obtained by the reaction formula 3 shown below; (III) in the reaction formula 1, (V) in the reaction formula 2, (VI) and (VIII) in the reaction formula 3 can be synthesized by purchasing or referring to relevant documents; l in the reaction formula 1, the reaction formula 2 and the reaction formula 3 may be the same or different and represents a leaving group of fluorine, chlorine, bromine or iodineEtc. in reaction formula 3 2 A salt of the compound represented by the formula (I) may be obtained by the reaction formula 4 shown below; the Acid in the reaction formula 4 is an organic Acid or an inorganic Acid, and other substituents are as defined above unless otherwise specified.
Reaction formula 1:
Figure GDA0003773939960000231
reaction formula 2:
Figure GDA0003773939960000232
reaction formula 3:
Figure GDA0003773939960000233
reaction formula 4:
Figure GDA0003773939960000234
the compounds of formula (I) may be prepared by (scheme 1): reacting a compound of formula (II) with a compound of formula (III) in a suitable solvent such as dichloromethane, dichloroethane, toluene, xylene, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, pyridine, tetrahydrofuran, methanol, ethanol, isopropanol, acetone, butanone, methyl isobutyl ketone, acetonitrile, ethyl acetate, dioxane or the like at a temperature of-10 ℃ to the reflux temperature of the system in the absence of a base or a suitable base which may be selected from alkali metal hydrides such as sodium hydride, with the reaction of formula (III) in the presence of a base which may be accelerated; alkali metal hydroxides such as sodium hydroxide or potassium hydroxide; alkali metal carbonates such as sodium carbonate or potassium carbonate; alkali metal alkoxides such as sodium methoxide or sodium ethoxide; organic amines, such as pyridine, triethylamine or diisopropylethylamine.
The compound of formula (II) may be prepared as follows (scheme 2): reacting a compound of formula (IV) with a compound of formula (V) in a suitable solvent such as dichloromethane, dichloroethane, toluene, xylene, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, pyridine, tetrahydrofuran, methanol, ethanol, isopropanol, acetone, butanone, methyl isobutyl ketone, acetonitrile, ethyl acetate, dioxane or the like at a temperature of-10 ℃ to the reflux temperature of the system in the absence of a base or a suitable base which may be selected from alkali metal hydrides such as sodium hydride to accelerate the reaction when the reaction is carried out in the presence of a base; alkali metal hydroxides such as sodium hydroxide or potassium hydroxide; alkali metal carbonates such as sodium carbonate or potassium carbonate; alkali metal alkoxides such as sodium methoxide or sodium ethoxide; organic amines, such as pyridine, triethylamine or diisopropylethylamine.
The compound of formula (IV) may be prepared by (reaction formula 3): reacting the compound of formula (VI) with a chlorinating agent such as chlorine or sulfonyl chloride at 0-50 deg.C in a solvent-free or suitable solvent such as ethyl acetate, dichloromethane, chloroform, dichloroethane, acetone, butanone or methyl isobutyl ketone, etc. to obtain a compound of formula (VII); reacting a compound of formula (VII) with a compound of formula (VIII) in a suitable solvent such as methanol, ethanol, propanol, isopropanol, dichloromethane, dichloroethane, toluene, xylene, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, pyridine, tetrahydrofuran, acetone, methyl ethyl ketone or methyl isobutyl ketone, etc., in the presence of a suitable base such as triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium hydroxide, potassium carbonate, sodium hydroxide or sodium carbonate, etc., at 5 ℃ to 50 ℃ to obtain a compound of formula (IX); reacting a compound of formula (IX) with a halogenating agent such as phosphorus oxychloride or phosphorus oxybromide in the presence of a suitable base such as triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium hydroxide, potassium carbonate, sodium hydroxide or sodium carbonate to give a compound of formula (IV);
salts of compounds of formula (I) may be prepared by (equation 4): reacting the compound of the formula (I) with Acid at the temperature of 0 ℃ to the reflux temperature of the system in one or two suitable solvents, wherein the suitable solvents are selected from dichloromethane, dichloroethane, trichloromethane, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, N-dimethylformamide, tetrahydrofuran, ethyl acetate, methanol, ethanol, isopropanol, dioxane and the like to obtain the compound salt of the formula (I).
Specific synthetic methods are set forth in more detail in the examples below.
The compound of formula (I) provided by the invention has broad-spectrum biological activity under the dosage of 7.5-2250 g of active ingredient per hectare, and can be used for preventing and controlling harmful germs and harmful insects or mites. Some compounds have good harmful germ prevention and treatment effects, and can obtain good effects at very low dosage.
The compound of formula (I) provided by the invention has bioactivity, and the compound has good bioactivity, and particularly shows activity in the aspects of preventing and controlling agricultural, horticultural, flower and sanitary pests and harmful bacteria. Pests as used herein include, but are not limited to:
harmful pathogenic bacteria: phytophthora species, erysiphe species, gibberella species, venturia species, sclerotinia species, rhizoctonia species, botrytis species, pyricularia species, fusarium species. Such as rice blast (Pyricularia oryzae); stripe rust (Puccinia striiformis), leaf rust (Puccinia recondita); barley and wheat powdery mildew (Erysiphe graminis), cucumber powdery mildew (Sphaerotheca fuligena), apple powdery mildew (podosphaea leucotricha) and grape powdery mildew (podosphaea leucotricha); sheath and glume blight of wheat (Septoria nodorum). Helminthosporium, mortierella, sclerotiella herpotrichoides, pseudocercospora herpotrichoides, and wheat take-all (Gaeumunnomyces graminis) on cereals. Cercospora arachidicola (Cercospora arachidicola) and Cercospora black spot (Cercospora personata); apple ring rot pathogen (Botryosphaeria berenggiana f.sp. Piricola), apple rot pathogen (cytopora sp.); urospora disease on beet, soybean and rice. Tomato, cucumber, grape gray mold (Botrytis cinerea). Diseases of the genus Geobacillus on vegetables such as cucumber. Anthracnose in cucumber, apple scab, cucumber downy mildew, grape downy mildew, blight in potato and tomato, the monad Thanatephorus cupmeris on rice and other rhizoctonia species on other hosts such as wheat and barley, vegetables; sclerotinia sclerotiorum (sclerotiorum); wheat scab (Gibberella zeae); phytophthora capsici (Phytophythora capsicii).
Harmful insects: lepidopteran pests such as oriental armyworm, prodenia litura, diamond back moth, beet armyworm, cabbage looper, orthopteran such as blattaria, thysanoptera such as cotton thrips, rice thrips, melon thrips, homopteran such as leafhopper, plant hopper, aphid, hymenopteran such as leaf bee larva, dipteran such as aedes, culex, fly; acarina pest mites such as panonychus citri, tetranychus urticae and the like.
The compounds of formula (I) of the present invention are effective for controlling pests, harmful bacteria, alone, and they can also be used together with other biochemical substances such as insecticides, nematocides, acaricides and bactericides.
Agricultural formulations containing the compound of formula (I) as an active ingredient provided by the present invention may be formulated into any desired dosage form, such as dry compressed granules, flowable compositions, granules, wettable powders, water dispersible granules, emulsifiable concentrates, powders, powder concentrates, microemulsions, suspensions, emulsifiable concentrates, aqueous emulsions, soluble liquids, aqueous solutions, dispersible liquids, suitable adjuvants including carrier diluents and other adjuvants such as spreaders, emulsifiers, wetting agents, dispersants, stickers and disintegrants. These formulations comprise the compounds of the present invention in admixture with an inert, pharmacologically acceptable solid or liquid diluent.
Examples of the compositions of the present invention may also be formulated into any desired dosage form such as dry compressed granules, flowable compositions, granules, wettable powders, water dispersible granules, emulsifiable concentrates, dusts, powdered concentrates, microemulsions, suspensions, emulsifiable concentrates, emulsions in water, soluble liquids, mists, dispersible liquids, suitable adjuvants including carrier diluents) and other adjuvants such as spreaders, emulsifiers, wetting agents, dispersants, stickers and disintegrants. These formulations comprise the compounds of the present invention in admixture with an inert, pharmacologically acceptable solid or liquid diluent.
The present invention will be further described with reference to the following examples, but the present invention is not limited thereto.
Synthetic examples
EXAMPLE 1 this example illustrates the preparation of compound I-A2-D1-1
Figure GDA0003773939960000251
After the quinazolin-4 (3H) -one anthranilic acid (0.25 mol) and formamide (1.00 mol) have reacted at 100-150 ℃ for 5-10H with stirring, the reaction mixture is treated with water at 50-80 ℃ with stirring, cooled, the solid filtered and recrystallized from ethanol to give 32.45g of the title compound.
4-chloroquinazolin-4 (3H) -one (0.15 mol), phosphorus pentachloride (0.21 mol) and phosphorus oxychloride (150 mL) are stirred and reacted for 15-25H under reflux conditions, after the phosphorus oxychloride is removed under reduced pressure, ethyl acetate and brine ice are added, the pH =7 is adjusted by amine water, an organic layer is separated, an aqueous layer is extracted by ethyl acetate, the organic layers are combined and washed by water, dried by anhydrous sodium sulfate, concentrated under reduced pressure, and a crude product is recrystallized by petroleum ether and ethyl acetate (V/V = 50/1) to obtain 13.2g of a title product.
(S) -2- ((quinazolin-4-yl) amino) propanol to a solution of 4-chloroquinazoline (20 mmol) and potassium carbonate (40 mmol) in N, N-dimethylformamide (20 mL) was added dropwise (S) -2-aminopropanol (30 mmol) at room temperature with stirring and stirred for 10-20h to completion. The reaction mixture was poured into ice water, extracted with ethyl acetate, and the organic layer was dried over anhydrous sodium sulfate, followed by removal of the solvent under reduced pressure to give the titled compound (3.29 g).
Adding sodium hydride (7.5 mmol) in batches to a solution of (S) -2- ((quinazolin-4-yl) amino) propanol (5 mmol) in N, N-dimethylformamide (10 mL) at 0-5 ℃ under stirring, stirring for 15-30min, adding 2,3-dichloropyridine (5 mmol) in batches, and naturally heating to room temperature for reacting for 8-16h to completion. The reaction was poured into ice water, extracted with ethyl acetate, the organic layer was dried over anhydrous sodium sulfate, the solvent was removed to give a crude product, which was subjected to column chromatography with petroleum ether and ethyl acetate V/V = 20-30) to give the title 0.85g.
EXAMPLE 1 this example illustrates the preparation of compound I-A7-D1-1
Figure GDA0003773939960000261
Adding 2- ((quinazoline-4-yl) amino) ethanol into a solution of 4-chloroquinazoline (20 mmol) and potassium carbonate (40 mmol) in N, N-dimethylformamide (20 mL) at room temperature under the stirring condition, dropwise adding 2-aminoethanol (30 mmol), and stirring for 10-20h until the reaction is complete. The reaction mixture was poured into ice water, extracted with ethyl acetate, and the organic layer was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure to give the title compound (3.19 g).
Adding sodium hydride (7.5 mmol) in batches into a solution of 2- ((quinazolin-4-yl) amino) ethanol (5 mmol) in N, N-dimethylformamide (10 mL) at 0-5 ℃ under the stirring condition, stirring for 15-30min, adding 2,3-dichloropyridine (5 mmol) in batches, and naturally heating to room temperature for reacting for 8-16h until the reaction is complete. The reaction was poured into ice water, extracted with dichloromethane, the organic layer was dried over anhydrous sodium sulfate, the solvent was removed to give the crude product, which was subjected to column chromatography with petroleum ether and ethyl acetate V/V = 20-30) to give the title 0.72g.
EXAMPLE 3 this example illustrates the preparation of IS-A2-D1-1-1 hydrochloride salt of Compound I-A2-D1-1
Figure GDA0003773939960000262
Adding hydrogen chloride (20 mmol) into a solution of (S) -N- (1- ((3-chloropyridin-2-yl) oxy) prop-2-yl) quinazolin-4-amine hydrochloride in ethyl acetate (10 mL) at 15-25 ℃ under stirring, continuing stirring until the reaction is complete, removing excess hydrogen chloride and solvent under reduced pressure, and washing and purifying the solvent to obtain a title compound.
The yields in the examples were not optimized, and other compounds of the present invention were synthesized by referring to examples 1 to 3, and if necessary, related references.
Preparation examples
Example 4 preparation of 10% tall oil
Weighing a proper amount of 10 percent by weight of the compound of the formula (I) provided by the invention, such as I-A2-D1-1, a proper amount of cosolvent, such as ethyl acetate or acetone), a proper amount of pesticide auxiliary agent, a solvent, such as toluene) and the like, putting the mixture into a reaction kettle, firstly adding a certain amount of solvent, such as toluene) and a defoaming agent, stirring for 10-30min, then adding a proper amount of components, such as a stabilizer, a synergist, a penetrating agent and the like, continuously stirring for 10-30min, regulating the PH value, then adding an effective amount of the solvent into the kettle, uniformly stirring, and then discharging to obtain 10 percent missible oil of the compound I-A2-D1-1.
EXAMPLE 5 preparation of 20% wettable powder
Weighing a proper amount of 20% by weight) of the compound of the formula (I), such as I-A2-D1-1, sodium dodecyl sulfate of 2% by weight, sodium lignosulfonate of 10% by weight, and kaolin which is complemented to 100% by weight, mixing together, and crushing in a crusher until the particles reach the standard.
Bioassay examples
The compound of the invention is subjected to bactericidal and insecticidal/acaricidal activity screening tests, and partial test results are as follows.
Example 6 insecticidal Activity against aphids (Aphis fabae)
The dipping method comprises the following steps: the test compound is dissolved in a suitable solvent such as acetone or N, N-dimethylformamide, diluted to the desired concentration with clear water containing 0.2% Tween80 emulsifier, and the blank containing no test compound is set as a control and the treatment is repeated 3 times. And (2) inoculating broad bean aphids on the bean seedlings which just come out of the soil, inoculating more than 20 heads on each bean seedling, then soaking the bean seedlings and the test insects in the compound liquid medicine of the formula (I) in the invention, taking out after 5 seconds, sucking off redundant liquid medicine, inserting the bean seedlings into absorbent sponge, covering the bean seedlings with a glass tube, checking the number of the living and dead insects after 24 hours, and averaging the results. Active mortality) is divided into A, B, C, D grades by percentage relative to a blank control, wherein the mortality of more than or equal to 90% in 100% is grade A, the mortality of more than 90% is grade B, the mortality of more than 70% is grade C, the mortality of more than 70% is grade 50%, and the mortality of more than 50% is grade D. Some of the results are listed below:
compounds I-A1-D1-1, I-A2-H1-1, I-A5-E1-1, I-A5-G1-1, I-A7-F1-1 and I-A7-J1-1, etc., have class A activity against aphids at a concentration of 500mg/L, and compounds I-A1-D1-1, I-A5-E1-1, I-A5-G1-1, I-A7-F1-1 and I-A7-J1-1, etc., have class B activity against aphids, and compounds I-A1-D1-38, I-A1-E1-38, I-A1-F1-38, I-A7-D1-1, I-A7-E1-1, I-A7-G1-1 and I-A8-E1-1, etc., class C activities such as I-A1-G1-1, I-A1-G1-38, I-A1-I1-38, and I-A7-I1-1, class D activities such as I-A1-H1-38, I-A1-I1-1, I-A7-E1-38, I-A7-G1-38, I-A7-I1-38, and I-A8-G1-1; under the same condition, the activity of D1 on aphids is D grade;
at the concentration of 50mg/L, the compounds I-A1-D1-1, I-A5-G1-1 and the like have A-level activity on aphids, and I-A2-D1-1, I-A2-H1-1 and the like have B-level activity;
at the concentration of 12.5mg/L, the compounds I-A1-D1-1, I-A5-G1-1 and the like have grade A activity on aphids.
Example 7 evaluation of acaricidal Activity against Tetranychus urticae
The method comprises the following steps: dissolving the compound in a suitable solvent such as N, N-dimethylformamide, diluting with water containing 0.2% Tween80 emulsifier to desired concentration, setting blank containing no test compound as blank, repeating each treatment for 3 times; selecting bean seedlings with good growth vigor to inoculate red spiders, cutting the bean seedlings with mites after the red spiders colonize, soaking the bean seedlings in the prepared liquid medicine of the compound shown in the formula (I) for 10 seconds, taking out the bean seedlings, absorbing the redundant liquid medicine by using filter paper, inserting the bean seedlings into a water-containing beaker, culturing the bean seedlings in an observation room, and checking the number of the alive and dead mites after 48 hours, wherein each bean seedling has 100-200 mites. The results were averaged. The activity was graded as in example 6. Some of the results are listed below:
at a concentration of 500mg/L, the compounds I-A1-G1-1, I-A2-H1-1, I-A5-E1-1, I-A5-G1-1 and I-A8-E1-1, etc. have class A activity against red spider, I-A1-D1-38, I-A1-E1-38, I-A1-F1-38, I-A1-G1-38, I-A1-H1-38, I-A1-I1-1, I-A1-I1-38, I-A7-D1-1, I-A7-E1-38, I-A7-F1-1, I-A7-G1-38, I-A7-H1-1, I-A7-I1-38, I-A7-J1-1, and I-A8-G1-1, etc. have D-level activity; under the same condition, the activity of D1 to red spider is D grade;
example 8 evaluation of biological Activity on armyworm (Mythimna separata)
A Potter spraying method: the test compound is dissolved in a suitable solvent such as N, N-dimethylformamide and diluted to the desired concentration with clear water containing 0.2% Tween80 emulsifier, and the blank containing no test compound is set as a control. Fresh and tender corn leaves are cut into segments with basically consistent sizes and placed into a culture dish (phi 90 mm) in which filter paper is placed in advance. Then 10 heads of mythimna separata larvae of 3 years old are inoculated into the dish, the dish is put under a Potter spray tower for quantitative spraying, the amount of the spraying liquid is 1ml, and the spraying is repeated for 3 times per concentration. And after the treatment is finished, covering the dish cover, placing the dish cover in a recovery room for culture, regularly observing, checking and recording the death condition of the test insects after 72 hours, calculating the death rate, and averaging the results. The activity was graded as in example 6. Some of the results are listed below:
at a concentration of 500mg/L, the compounds I-A1-G1-1, I-A1-I1-1, I-A5-E1-1, I-A5-G1-1, I-A7-K1-38, I-A7-L1-38, etc. have class A activity against armyworms, I-A7-H1-1, etc. have class B activity, I-A7-D1-1, I-A8-E1-1, etc. have class C activity, I-A1-D1-38, I-A1-E1-38, I-A1-F1-38, I-A1-I1-38, I-A7-E1-1, I-A7-E1-38, I-A7-F1-1, I-A7-G1-38, I-A1-H1-38, I-A7-I1-1, I-A7-I1-38, I-A7-J1-1, and I-A8-G1-1, etc., have D-class activity; under the same condition, the activity of D1 to armyworm is B grade;
under the concentration of 200mg/L, the compound I-A5-G1-1 and the like have A-level activity on armyworms, and the compound I-A5-E1-1 and the like have B-level activity;
at a concentration of 50mg/L, the compound I-A5-G1-1 and the like have B-level activity on armyworms.
Example 9 fungicidal Activity against wheat powdery mildew (Erisiphe grimmins)
Pot culture method: dissolving the test compound in a suitable solvent such as N, N-dimethylformamide, and diluting with sterile water containing 0.2% Tween80 emulsifier to the desired concentration; taking pots with straight stems of about 15cm, sowing 20 plump and robust seeds of wheat in each pot, and allowing the wheat to grow into two leaves and one heart for testing; spraying the prepared wheat seedling plant with a medicament with a certain concentration, and inoculating germs after one day. Repeating the treatment for 3 times, and additionally setting a blank without the compound to be detected as a blank contrast and a commercial fungicide flusilazole as a commercial contrast; and (5) after the culture is carried out in a moisture-preserving and temperature-adapting way until blank control is carried out, checking the area of the lesion spots and calculating the control effect of the medicament. The activity of the composition is classified into A, B, C, D grade four in percentage relative to a blank control, wherein 100% and 90% of the prevention effect are grade A, 90% and 70% of the prevention effect are grade B, 70% and 50% of the prevention effect are grade C, and 50% and 0% of the prevention effect are grade D. Some of the results are as follows:
at a concentration of 500mg/L, the compounds I-A1-D1-1, I-A1-E1-1, I-A1-G1-1, I-A1-I1-1, I-A2-D1-1, I-A2-H1-1, I-A5-G1-1, I-A8-E1-1, etc. have class A activity against wheat powdery mildew, and I-A7-J1-1, etc. have class C activity, I-A1-D1-38, I-A1-E1-38, I-A1-F1-38, I-A1-G1-38, I-A1-H1-38, I-A1-I1-38, I-A7-E1-1, I-A7-E1-38, I-A7-G1-1, I-A7-G1-38, I-A7-H1-1, I-A7-I1-38, and I-A8-G1-1, etc., have D-class activity; under the same conditions, D1 has grade A activity on wheat powdery mildew;
at the concentration of 50mg/L, the compounds I-A2-D1-1, I-A8-E1-1 and the like have B-level activity on wheat powdery mildew, and the compounds I-A1-D1-1, I-A2-H1-1, I-A5-G1-1 and the like have C-level activity; under the same conditions, the activity of D1 on wheat powdery mildew is grade D.
I-A2-D1-1 and the like are selected for deep screening, and the results show that the ED of the compound I-A2-D1-1 and the like on wheat powdery mildew 50 ED values lower than 2.50mg/L, I-A8-E1-1, etc 50 The value is 2.50-5.00mg/L; ED of Flusilazole against wheat powdery mildew under the same conditions 50 The value was less than 2.50mg/L.
Example 10 fungicidal Activity against corn rust Puccinia Polysora)
Pot culture method: dissolving the compound in a suitable solvent such as N, N-dimethylformamide, diluting with sterile water containing 0.2% Tween80 emulsifier to desired concentration, and setting blank containing no compound to be tested as blank control and commercial bactericide tebuconazole as commercial control; repeat 4 times per treatment; cutting diseased corn leaf, washing spore with 0.05% Tween80 or other suitable surfactant aqueous solution, filtering with 2-4 layers of gauze to obtain a concentration of 1 × 10 5 spore/mL of suspension; spraying the liquid medicine of the compound to be detected when the corn grows to 2 leaves and 1 heart stage, 1Spraying and inoculating the spore suspension liquid after days, transferring the spore suspension liquid to a moisturizing cabinet after inoculation, wherein the relative humidity is more than 95%, the temperature is 20-22 ℃, and the illumination intensity is 5000Lux-10000 Lux) under the weak light condition for culturing for 15-24 hours; and when the blank control disease leaf rate reaches more than 50%, investigating the disease condition of each treatment, and calculating the control effect. The activity was graded as in example 9. The result shows that the compound has control effect on the corn rust. The following are partial results:
at the concentration of 500mg/L, the compounds I-A1-E1-1, I-A1-G1-1, I-A1-I1-1, I-A2-D1-1, I-A5-E1-1, I-A5-G1-1 and the like have grade A activity on corn rust, I-A7-J1-1 and the like have grade B activity, I-A1-E1-38, I-A1-F1-38, I-A1-D1-38, I-A1-G1-38, I-A1-H1-38, I-A7-I1-1, I-A1-I1-38, I-A7-E1-1, I-A7-E1-38, I-A7-F1-1, I-A7-G1-38, I-A7-H1-1, I-A7-I1-38, I-A8-E1-1, and I-A8-G1-1, etc. have D-level activity; under the same condition, the activity of D1 to the corn rust is A grade;
under the concentration of 50mg/L, the compound I-A2-D1-1 and the like have B-grade activity on corn rust; under the same conditions, D1 has no activity on corn rust;
I-A2-D1-1 and the like are selected for deep screening, and the results show that the compound I-A2-D1-1 and the like have ED (effective component) against corn rust 50 Values below 5.00mg/L; ED of tebuconazole under the same conditions 50 The value was less than 5.00mg/L.
Example 11 fungicidal Activity against Rhizoctonia solani) of Rice sheath blight disease
Pot culture method: dissolving the test compound in a suitable solvent such as N, N-dimethylformamide, diluting with sterile water containing 0.2% Tween80 emulsifier to the desired concentration, and repeating the treatment for 4 times, with blank containing no test compound as control; transferring the rhizoctonia solani pathogenic bacteria to a PDA flat plate for activation culture, transferring the rhizoctonia solani pathogenic bacteria to a PD culture medium, and culturing for 4 days in a constant-temperature water bath. And crushing the cultured mycelium pellets by using a homogenizer and preparing the mycelium pellets into bacterial suspension with a certain concentration by using clear water. The cucumber was used for the experiment when it had grown to flatten two cotyledons. Spraying the liquid medicine, spraying the bacterial suspension to the surface of the seedling after 24 hours, and performing moisturizing culture. And observing the disease occurrence condition of the seedlings, and when the disease occurrence condition of the control treatment is obvious, beginning to investigate the disease occurrence condition of each treatment and calculating the medicament control effect. The activity was graded as in example 9. The results show that the compound has the effect of preventing and treating the rice sheath blight disease. If the concentration is 500mg/L, the compound I-A7-L1-38 and the like have C-grade control effect on rice sheath blight; under the same conditions, D1 has no control effect on rice sheath blight disease.

Claims (6)

1. Quinazoline-containing aza-ether compounds with biological activity,
Figure FDA0003806242880000011
characterized in that the compound of formula (I) is:
(RS) -N- (1- ((3-chloropyridin-2-yl) oxy) prop-2-yl) quinazolin-4-amine;
(RS) -N- (1- ((3-chloropyridin-2-yl) oxy) prop-2-yl) -6,7-dimethoxyquinazolin-4-amine;
(RS) -N- (1- ((5-trifluoromethylpyridin-2-yl) oxy) prop-2-yl) -6,7-dimethoxyquinazolin-4-amine;
(RS) -N- (1- ((3,5-dichloropyridin-2-yl) oxy) propan-2-yl) -6,7-dimethoxyquinazolin-4-amine;
(RS) -N- (1- ((3-chloro-5-trifluoromethylpyridin-2-yl) oxy) prop-2-yl) quinazolin-4-amine;
(RS) -N- (1- ((3-chloro-5-trifluoromethylpyridin-2-yl) oxy) prop-2-yl) -6,7-dimethoxyquinazolin-4-amine;
(RS) -N- (1- ((3-fluoro-5-chloropyridin-2-yl) oxy) prop-2-yl) quinazolin-4-amine;
(RS) -N- (1- ((3-fluoro-5-chloropyridin-2-yl) oxy) prop-2-yl) -6,7-dimethoxyquinazolin-4-amine;
(S) -N- (1- ((3-chloropyridin-2-yl) oxy) prop-2-yl) quinazolin-4-amine;
(S) -N- (1- ((3,5,6-trichloropyridin-2-yl) oxy) prop-2-yl) quinazolin-4-amine;
(S) -N- (1- ((5-trifluoromethylpyridin-2-yl) oxy) but-2-yl) quinazolin-4-amine;
(S) -N- (1- ((3-chloro-5-trifluoromethylpyridin-2-yl) oxy) but-2-yl) quinazolin-4-amine;
n- (2- ((3-chloropyridin-2-yl) oxy) ethyl) quinazolin-4-amine;
n- (2- ((5-trifluoromethylpyridin-2-yl) oxy) ethyl) quinazolin-4-amine;
n- (2- ((3,5-dichloropyridin-2-yl) oxy) ethyl) quinazolin-4-amine;
n- (2- ((3-chloro-5-trifluoromethylpyridin-2-yl) oxy) ethyl) quinazolin-4-amine;
n- (2- ((3-fluoro-5-chloropyridin-2-yl) oxy) ethyl) quinazolin-4-amine;
n- (2- ((6-trifluoromethylpyridin-2-yl) oxy) ethyl) quinazolin-4-amine;
n- (2- ((3-nitro-6-chloropyridin-2-yl) oxy) ethyl) -6,7-dimethoxyquinazolin-4-amine;
n- (2- ((3-nitro-6-methoxypyridin-2-yl) oxy) ethyl) -6,7-dimethoxyquinazolin-4-amine.
2. The method for preparing quinazoline-containing aza ethers as claimed in claim 1, wherein the compound of formula (I) is prepared by the reaction shown below:
reaction formula 1:
Figure FDA0003806242880000012
reaction formula 2:
Figure FDA0003806242880000021
reacting a compound of formula (II) with a compound of formula (III) in the solvents dichloromethane, dichloroethane, toluene, xylene, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, pyridine, tetrahydrofuran, methanol, ethanol, isopropanol, acetone, butanone, methyl isobutyl ketone, acetonitrile, ethyl acetate or dioxane at a temperature of-10 ℃ to the system reflux temperature in the absence of a base or a suitable base selected from the group consisting of sodium hydride, sodium hydroxide or potassium hydroxide, sodium carbonate or potassium carbonate, sodium methoxide or sodium ethoxide, organic amines pyridine, triethylamine or diisopropylethylamine;
reacting a compound of formula (IV) with a compound of formula (V) in the solvent dichloromethane, dichloroethane, toluene, xylene, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, pyridine, tetrahydrofuran, methanol, ethanol, isopropanol, acetone, butanone, methyl isobutyl ketone, acetonitrile, ethyl acetate or dioxane at a temperature of-10 ℃ to the system reflux temperature in the absence of a base or a suitable base selected from the group consisting of sodium hydride alkali metal hydroxides, sodium hydroxide or potassium hydroxide, sodium carbonate or potassium carbonate alkali metal carbonates, sodium methoxide or sodium ethoxide alkali metal alkoxides, organic aminopyridine, triethylamine or diisopropylethylamine;
wherein R, R 1 、R 2 M, A, X, V have the meanings given in claim 1, L is a leaving group fluorine, chlorine, bromine or iodine.
3. Use of quinazoline-containing aza-ethers as claimed in claim 1 characterised by insecticidal/acaricidal or fungicidal biological activity at a dose of 7.5-2250 g active ingredient/ha.
4. Use of the quinazoline containing azaethers of claim 1 in the manufacture of a medicament with insecticidal/acaricidal or fungicidal activity.
5. An insecticidal/acaricidal or fungicidal composition comprising: contains the quinazoline-containing aza-ether compound as claimed in claim 1 as an active ingredient and an acceptable carrier, wherein the weight percentage of the active ingredient in the composition is 0.5-90%.
6. A method for controlling pests/mites or harmful germs, which is not disease diagnosis and treatment, characterized in that: applying an effective amount of the quinazoline-containing azaether compounds of claim 1 to said pest/mite, pest pathogen, or growth medium thereof.
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2043061A (en) * 1979-03-05 1980-10-01 Ici Ltd Thienopyrimidine and quinazoline derivatives
JPH07118242A (en) * 1993-10-26 1995-05-09 Ube Ind Ltd Phenoxyalkylamine derivative, its manufacturing method and pest control agent for agriculture and horticulture
US5668140A (en) * 1991-05-17 1997-09-16 Hoechst Aktiengesellschaft Substituted 4-aminopyrimidines, processes for their preparation, and their use as pesticides
JP2002316979A (en) * 2001-02-19 2002-10-31 Ube Ind Ltd 6- (1-Fluoroethyl) -5-iodo-4-aminopyrimidine compound, production method thereof and pesticide for agricultural and horticultural use
CN106167484A (en) * 2015-05-18 2016-11-30 沈阳中化农药化工研发有限公司 Substituted pyrazolecarboxylic compounds containing pyrimidine and its production and use
CN107840825A (en) * 2016-09-21 2018-03-27 湖南化工研究院有限公司 Seven fluorine isopropyl quinoline class compounds and preparation method and application
CN108069973A (en) * 2016-11-18 2018-05-25 沈阳中化农药化工研发有限公司 Substitution hexa-member heterocycle class compound of the ring containing pyrimido and its preparation method and application
CN109776427A (en) * 2017-11-13 2019-05-21 沈阳中化农药化工研发有限公司 Double aminated compounds of pyrimidine and application thereof
CN111004218A (en) * 2018-10-08 2020-04-14 沈阳中化农药化工研发有限公司 Piperidine-containing pyrimidine compound and application thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2043061A (en) * 1979-03-05 1980-10-01 Ici Ltd Thienopyrimidine and quinazoline derivatives
US5668140A (en) * 1991-05-17 1997-09-16 Hoechst Aktiengesellschaft Substituted 4-aminopyrimidines, processes for their preparation, and their use as pesticides
JPH07118242A (en) * 1993-10-26 1995-05-09 Ube Ind Ltd Phenoxyalkylamine derivative, its manufacturing method and pest control agent for agriculture and horticulture
JP2002316979A (en) * 2001-02-19 2002-10-31 Ube Ind Ltd 6- (1-Fluoroethyl) -5-iodo-4-aminopyrimidine compound, production method thereof and pesticide for agricultural and horticultural use
CN106167484A (en) * 2015-05-18 2016-11-30 沈阳中化农药化工研发有限公司 Substituted pyrazolecarboxylic compounds containing pyrimidine and its production and use
CN107840825A (en) * 2016-09-21 2018-03-27 湖南化工研究院有限公司 Seven fluorine isopropyl quinoline class compounds and preparation method and application
CN108069973A (en) * 2016-11-18 2018-05-25 沈阳中化农药化工研发有限公司 Substitution hexa-member heterocycle class compound of the ring containing pyrimido and its preparation method and application
CN109776427A (en) * 2017-11-13 2019-05-21 沈阳中化农药化工研发有限公司 Double aminated compounds of pyrimidine and application thereof
CN111004218A (en) * 2018-10-08 2020-04-14 沈阳中化农药化工研发有限公司 Piperidine-containing pyrimidine compound and application thereof

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