CN112778192B - Polyfluoroalkyl-containing isoindolinone benzamide derivatives, and preparation method and application thereof - Google Patents

Polyfluoroalkyl-containing isoindolinone benzamide derivatives, and preparation method and application thereof Download PDF

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CN112778192B
CN112778192B CN201911074903.3A CN201911074903A CN112778192B CN 112778192 B CN112778192 B CN 112778192B CN 201911074903 A CN201911074903 A CN 201911074903A CN 112778192 B CN112778192 B CN 112778192B
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benzamide
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许天明
邢家华
赵灵杰
魏优昌
黄红英
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Zhejiang Chemical Industry Research Institute Co Ltd
Sinochem Lantian Co Ltd
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Sinochem Lantian Co Ltd
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    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/46—Iso-indoles; Hydrogenated iso-indoles with an oxygen atom in position 1
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A01N43/38—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings condensed with carbocyclic rings

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Abstract

The invention provides polyfluoroalkyl-containing isoindolinone benzamide derivatives which have the following general formula A-1:

Description

Polyfluoroalkyl-containing isoindolinone benzamide derivatives, and preparation method and application thereof
Technical Field
The invention belongs to the field of agricultural pesticides, and particularly relates to a substituted benzamide derivative.
Background
The long-term use of the existing pesticide varieties causes the diseases to generate resistance to the existing pesticide varieties, so that new pesticide varieties with different action mechanisms are required to be continuously discovered. The excessive use of the existing pesticide brings more pressure to the environment, so that the development of new pesticide varieties with higher efficiency is required.
In recent years, as the technology of fluorine chemistry has been improved, more and more perfluoro groups have been introduced into organic compounds. By effectively utilizing the unique physical and chemical properties of fluorine atoms, such as pseudo effect, blocking effect, high electronegativity, fat solubility and the like, a novel organic compound introduced with a perfluoro group can have unique performance, and further a novel pesticide variety can be developed.
For the novel compounds having insecticidal activity which incorporate fluorine-containing heterocyclic groups, the following are reported in the prior art:
PCT patent applications WO2010015355, WO2012069366, WO2010127926, WO2010127928, WO 201702629, WO2015097091, WO2015097094, WO2015133603 disclose polyfluoroalkyl-containing benzamide compounds, which have insecticidal activity and can be developed as agricultural insecticides.
Polyfluoroalkyl-containing isoindolinone benzamide compounds are not disclosed in the prior art.
Disclosure of Invention
The invention aims to provide polyfluoroalkyl-containing isoindolinone benzamide derivatives which have the following general formula A-1:
Figure BDA0002262135340000021
the substituent groups R1, R2 and R3 of the polyfluoroalkyl-containing isoindolinone benzamide derivative shown in the general formula A-1 provided by the invention can be independently selected from hydrogen, halogen, nitryl, nitrile group, C1-C20 alkyl, C1-C20 halogenated alkyl, C1-C20 naphthenic base, C1-C20 halogenated naphthenic base, C1-C20 alkyl alkenyl, C1-C20 alkoxy, C1-C20 halogenated alkoxy, C1-C20 alkylthio, C1-C20 halogenated alkylthio, C1-C20 alkyl sulfoxide group and C1-C20 alkyl sulfone group.
As a preferable mode, R1, R2 and R3 are independently selected from hydrogen, halogen, nitro, nitrile group, C1-C10 alkyl, C1-C10 haloalkyl, C1-C10 cycloalkyl, C1-C10 halocycloalkyl, C1-C10 alkenyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C1-C10 alkylthio, C1-C10 haloalkylthio, C1-C10 alkylsulfoxide group and C1-C10 alkylsulfone group.
As another preferred mode, R1, R2 and R3 are independently selected from hydrogen, halogen, nitro, nitrile group, C1-C5 alkyl, C1-C5 haloalkyl, C1-C5 cycloalkyl, C1-C5 halocycloalkyl, C1-C5 alkanyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C1-C5 alkylthio, C1-C5 haloalkylthio, C1-C5 alkylsulfoxide and C1-C5 alkylsulfone.
In still another preferred mode, R1, R2, R3 are independently selected from the group consisting of hydrogen, fluorine, chlorine, bromine, nitro, nitrile, methyl, ethyl, isopropyl, trifluoromethyl, methoxy, ethoxy, methylthio, ethylthio, methylsulfonyl, ethylsulfoxide, methylsulfonyl, ethylsulfone, trifluoromethylsulfone, trifluoromethylsulfoxide, trifluoroethylsulfoxide, and trifluoroethylethylsulfone.
The substituent R4 of the polyfluoroalkyl-containing isoindolinone benzamide derivative shown in the general formula A-1 provided by the invention is selected from hydrogen, halogen, nitryl, nitrile group, C1-C20 alkyl, C1-C20 halogenated alkyl, C1-C20 naphthenic base, C1-C20 halogenated naphthenic base, C1-C20 alkyl alkenyl, C1-C20 alkoxy, C1-C20 halogenated alkoxy, C1-C20 alkylthio, C1-C20 halogenated alkylthio, C1-C20 alkyl sulfoxide group and C1-C20 alkyl sulfone group.
In a preferred mode, R4 is selected from hydrogen, halogen, nitro, nitrile group, C1-C10 alkyl, C1-C10 haloalkyl, C1-C10 cycloalkyl, C1-C10 halocycloalkyl, C1-C10 alkenyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C1-C10 alkylthio, C1-C10 haloalkylthio, C1-C10 alkylsulfoxide, and C1-C10 alkylsulfoxide.
As another preferred mode, R4 is selected from the group consisting of hydrogen, halogen, nitro, nitrile, C1-C5 alkyl, C1-C5 haloalkyl, C1-C5 cycloalkyl, C1-C5 halocycloalkyl, C1-C5 alkanyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C1-C5 alkylthio, C1-C5 haloalkylthio, C1-C5 alkylsulfinyl, C1-C5 alkylsulfonyl.
In still another preferred embodiment, R4 is selected from the group consisting of hydrogen, fluorine, chlorine, bromine, nitro, nitrile, methyl, ethyl, isopropyl, trifluoromethyl, methoxy, ethoxy, methylthio, ethylthio, methylsulfonyl, ethylsulfoxyl, methylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl, trifluoromethylsulfoxyl, trifluoroethylsulfoxyl, and trifluoroethylylsulfonyl.
The invention provides the polyfluoroalkyl-containing isoindolinone benzamide derivative shown in the general formula A-1, wherein a substituent R5 is selected from hydrogen, halogen, nitro, nitrile group, C1-C20 alkyl, C1-C20 halogenated alkyl, C1-C20 cycloalkyl, C1-C20 halogenated cycloalkyl, C1-C20 alkenyl, C1-C20 alkoxy, C1-C20 halogenated alkoxy, C1-C20 alkylthio and C1-C20 halogenated alkylthio.
In a preferred mode, R5 is selected from the group consisting of hydrogen, halogen, nitro, nitrile, C1-C10 alkyl, C1-C10 haloalkyl, C1-C10 cycloalkyl, C1-C10 halocycloalkyl, C1-C10 alkanyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C1-C10 alkylthio, and C1-C10 haloalkylthio.
As another preferred mode, R5 is selected from the group consisting of hydrogen, halogen, nitro, nitrile, C1-C5 alkyl, C1-C5 haloalkyl, C1-C5 cycloalkyl, C1-C5 halocycloalkyl, C1-C5 alkalkenyl, C1-C5 alkoxy, C1-C5 haloalkoxy, C1-C5 alkylthio, and C1-C5 haloalkylthio.
In still another preferred embodiment, R5 is selected from the group consisting of hydrogen, fluorine, chlorine, bromine, nitro, nitrile, methyl, ethyl, isopropyl, trifluoromethyl, methoxy, ethoxy, methylthio, ethylthio, methylsulfonyl, ethylsulfoxyl, methylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl, trifluoromethylsulfoxyl, trifluoroethylsulfoxyl, and trifluoroethylylsulfonyl.
The invention provides the polyfluoroalkyl-containing isoindolinone benzamide derivative shown in the general formula A-1, wherein a substituent R is selected from hydrogen, C1-C20 alkyl, C1-C20 halogenated alkyl and C1-C20 alkenyl.
In a preferred embodiment, R is selected from the group consisting of hydrogen, C1-C10 alkyl, C1-C10 haloalkyl, C1-C10 alkylalkenyl.
As another preferred mode, R is selected from the group consisting of hydrogen, C1-C5 alkyl, C1-C5 haloalkyl, C1-C5 alkanyl.
In still another preferred embodiment, R is selected from hydrogen, methyl, ethyl, and isopropyl.
The polyfluoroalkyl-containing isoindolinone benzamide derivative shown in the general formula A-1 provided by the invention has n selected from an integer of 0-4.
In a preferred embodiment, n is an integer of 0 to 2.
In a more preferred embodiment, the polyfluoroalkyl-containing isoindolinone benzamide derivative represented by the general formula A-1 is selected from at least one of the following compounds:
Figure BDA0002262135340000051
as an example, the polyfluoroalkyl-containing isoindolinone benzamide derivative represented by the above general formula A-1 may include compounds described in the following Table 1.
TABLE 1 partial compound List
Figure BDA0002262135340000052
Figure BDA0002262135340000061
Figure BDA0002262135340000071
Figure BDA0002262135340000081
The physical properties of some of the compounds described in table 1 above are as follows:
n- (4- (heptafluoroisopropyl-2-yl) phenyl) -3- (1-oxoisoindolin-2-yl) benzamide (ZJ-1) m.p.250-252 ℃. 1 H NMR(600MHz,CDCl 3 )δ:4.86(s,2H,N-CH 2 ),7.47(t,J＝7.9Hz,1H),7.50–7.53(m,2H,Ph-H),7.60–7.66(m,4H,Ph-H),7.89(d,J＝8.5Hz,3H,Ph-H),7.96–7.98(m,1H,Ph-H),8.37(t,J＝2.0Hz,1H,Ph-H),8.66(s,1H,CONH)；ESI-MS calcd for C 24 H 16 F 7 N 2 O 2 ([M+H] + )497,found 497.；
N- (2-methyl-4- (heptafluoroisopropyl-2-yl) phenyl) -3- (1-oxoisoindolin-2-yl) benzamide (ZJ-2): m.p.232-235 ℃; 1 H NMR(600MHz,CDCl 3 )2.45(s,3H,CH 3 ),4.87(s,2H,N-CH 2 ),7.47–7.52(m,5H,Ph-H),7.57–7.68(m,2H,Ph-H),7.82–8.08(m,2H,Ph-H),8.15–8.24(m,2H,Ph-H),8.48(s,1H,CONH)；ESI-MS calcd for C 25 H 18 F 7 N 2 O 2 ([M+H] + )511,found 511.；
n- (2-methyl)Oxy-4- (heptafluoroisopropyl-2-yl) phenyl) -3- (1-oxoisoindolin-2-yl) benzamide (ZJ-3): m.p.201-203 ℃; 1 H NMR(600MHz,CDCl 3 )δ:4.01(s,3H,OCH 3 ),4.95(s,2H,N-CH 2 ),7.12(d,J＝2.0Hz,1H,Ph-H),7.28(d,J＝8.7Hz,1H,Ph-H),7.51–7.60(m,3H,Ph-H),7.64(td,J＝7.5,1.2Hz,2H,Ph-H),7.95(d,J＝7.6Hz,1H,Ph-H),8.30–8.36(m,2H,Ph-H),8.67(d,J＝8.6Hz,1H,Ph-H),8.70(s,1H,CONH)；ESI-MS calcd for C 25 H 18 F 7 N 2 O 3 ([M+H] + )527,found 527.；
n- (2-chloro-4- (heptafluoroisopropyl-2-yl) phenyl) -3- (1-oxoisoindolin-2-yl) benzamide (ZJ-4): m.p.206-208 ℃; 1 H NMR(600MHz,CDCl 3 )δ:4.96(s,2H,N-CH 2 ),7.53–7.62(m,4H,Ph-H),7.64(td,J＝7.5,1.2Hz,1H,Ph-H),7.67–7.71(m,2H,Ph-H),7.96(dt,J＝7.6,1.0Hz,1H,Ph-H),8.28(ddd,J＝8.2,2.3,0.9Hz,1H,Ph-H),8.46(t,J＝2.0Hz,1H,Ph-H),8.66(s,1H,CONH),8.78(d,J＝8.6Hz,1H,Ph-H)；ESI-MS calcd for C 24 H 14 ClF 7 N 2 NaO 2 ([M+Na] + )553,found 553.；
n- (2, 6-dimethyl-4- (heptafluoroisopropyl-2-yl) phenyl) -3- (1-oxoisoindolin-2-yl) benzamide (ZJ-5): m.p.228-230 ℃; 1 H NMR(600MHz,CDCl 3 )δ:2.38(s,6H,CH 3 ),4.96(s,2H,N-CH 2 ),7.37(s,2H,Ph-H),7.53–7.61(m,3H,Ph-H),7.65(td,J＝7.5,1.0Hz,1H,Ph-H),7.75(d,J＝7.8Hz,1H,Ph-H),7.78(s,1H,Ph-H),7.94(d,J＝7.6Hz,1H,Ph-H),8.09(ddJ＝8.2,1.5Hz,1H,Ph-H),8.56(s,1H,CONH)； 19 F NMR(564MHz,CDCl 3 )δ:-182.25–-181.11(m,1F),-75.44(d,J＝7.6Hz,6F)；ESI-MS calcd for C 26 H 20 F 7 N 2 O 2 ([M+H] + )525,found 525.；
n- (2, 5-dimethyl-4- (heptafluoroisopropyl-2-yl) phenyl) -3- (1-oxoisoindolin-2-yl) -benzamide (ZJ-6): m.p.214-216 ℃; 1 H NMR(600MHz,CDCl 3 )δ:2.39(s,3H,CH 3 ),2.53(d,J＝8.9Hz,3H,CH 3 ),4.95(s,2H,N-CH 2 ),7.32(s,1H,Ph-H),7.52–7.60(m,3H,Ph-H),7.65(td,J＝7.5,1.2Hz,1H,Ph-H),7.69(dt,J＝7.6,0.9Hz,1H,Ph-H),7.91–7.96(m,2H,Ph-H),8.08(s,1H,CONH),8.11(ddd,J＝8.2,2.3,1.0Hz,1H,Ph-H),8.53(t,J＝2.0Hz,1H,Ph-H)；ESI-MS calcd for C 26 H 20 F 7 N 2 O 2 ([M+H] + )525,found 525.；
n- (2-methyl-6-ethyl-4- (heptafluoroisopropyl-2-yl) phenyl) -3- (1-oxoisoindolin-2-yl) benzamide (ZJ-7): m.p.185-187 deg.C; 1 H NMR(600MHz,CDCl 3 )δ:1.22(t,J＝7.7Hz,3H,CH 2 CH 3 ),2.35(s,3H,Ph-CH 3 ),2.71(q,J＝7.7Hz,2H,CH 2 CH 3 ),4.92(s,2H,N-CH 2 ),7.37(s,2H,Ph-H),7.51–7.56(m,3H,Ph-H),7.63(t,J＝7.5Hz,1H,Ph-H),7.73(d,J＝7.6Hz,1H,Ph-H),7.90(d,J＝7.2Hz,2H,Ph-H),8.10(d,J＝8.2Hz,1H,Ph-H),8.52(s,1H,CONH)；ESI-MS calcd for C 27 H 22 F 7 N 2 O 2 ([M+H] + )539,found 539.；
n- (2-bromo-6-methyl-4- (heptafluoroisopropyl-2-yl) phenyl) -3- (1-oxoisoindolin-2-yl) benzamide (ZJ-8): m.p.194-196 ℃; 1 H NMR(600MHz,CDCl 3 )δ:2.45(s,3H,CH 3 ),4.97(s,2H,N-CH 2 ),7.50(s,1H,Ph-H),7.53–7.58(m,2H,Ph-H),7.61(t,J＝8.0Hz,1H,Ph-H),7.65(td,J＝7.4,1.1Hz,1H,Ph-H),7.74(s,1H,Ph-H),7.77(d,J＝7.7Hz,1H,Ph-H),7.91(s,1H,Ph-H),7.95(d,J＝7.6Hz,1H,Ph-H),8.20(dd,J＝8.2,2.0Hz,1H,Ph-H),8.53(s,1H,CONH)；ESI-MS calcd for C 25 H 17 BrF 7 N 2 O 2 ([M+H] + )589,found 589.；
n- (2-bromo-6-ethyl-4- (heptafluoroisopropyl-2-yl) phenyl) -3- (1-oxoisoindolin-2-yl) benzamide (ZJ-9): m.p.208-210 ℃; 1 H NMR(600MHz,CDCl 3 )δ:1.27(t,J＝7.6Hz,3H,CH 2 CH 3 ),2.80(q,J＝7.5Hz,2H,CH 2 CH 3 ),4.97(s,2H,N-CH 2 ),7.53(s,1H,Ph-H),7.53–7.58(m,2H,Ph-H),7.60(t,J＝8.0Hz,1H,Ph-H),7.65(td,J＝7.5,1.0Hz,1H,Ph-H),7.79–7.73(m,2H,Ph-H),7.92(s,1H,Ph-H),7.95(d,J＝7.6Hz,1H,Ph-H),8.17(dd,J＝8.2,1.5Hz,1H,Ph-H),8.53(s,1H,CONH)；ESI-MS calcd for C 26 H 19 BrF 7 N 2 O 2 ([M+H] + )603,found 603.；
n- (4- (heptafluoroisopropyl-2-yl) phenyl) -2-fluoro-3- (1-oxoisoindolin-2-yl) benzamide (ZJ-10): m.p.276-278 ℃; 1 H NMR(600MHz,CDCl 3 )δ:4.90(s,2H,N-CH 2 ),7.41(t,J＝7.9Hz,1H,Ph-H),7.55–7.58(m,2H,Ph-H),7.61(d,J＝8.7Hz,2H,Ph-H),7.67(td,J＝7.5,1.2Hz,1H,Ph-H),7.72(td,J＝7.6,1.8Hz,1H,Ph-H),7.82(d,J＝8.7Hz,2H,Ph-H),7.98(d,J＝7.6Hz,1H,Ph-H),8.07(t,J＝7.4Hz,1H,Ph-H),8.63(d,J＝12.0Hz,1H,；ESI-MS calcd for C 24 H 14 F 8 N 2 NaO 2 ([M+Na] + )537,found 537.；
n- (2-methyl-4- (heptafluoroisopropyl-2-yl) phenyl) -2-fluoro-3- (1-oxoisoindolin-2-yl) benzamide (ZJ-11): m.p.254-257 ℃; 1 H NMR(600MHz,CDCl 3 )δ:2.40(s,3H,CH 3 ),4.90(s,2H,N-CH 2 ),7.41(t,J＝7.9Hz,1H,Ph-H),7.46(s,1H,Ph-H),7.51(d,J＝8.7Hz,1H,Ph-H),7.56(td,J＝7.5,1.0Hz,2H,Ph-H),7.66(td,J＝7.5,1.2Hz,1H,Ph-H),7.73(td,J＝7.7,1.8Hz,1H,Ph-H),7.98(d,J＝7.3Hz,1H,Ph-H),8.12(t,J＝6.8Hz,1H,Ph-H),8.35(d,J＝8.7Hz,1H,Ph-H),8.53(d,J＝13.6Hz,1H,CONH)； 13 C NMR(150MHz,CDCl 3 )δ:18.06,52.37,91.34(dq,J＝202.6,34.1Hz),120.68(qd,J＝286.5,27.7Hz,2C),122.41,122.72,122.86,122.94,123.01,124.51,125.32(d,J＝3.8Hz),126.65(d,J＝13.1Hz),127.68(d,J＝11.1Hz),128.55,128.76,130.91,131.38,132.25,132.48,138.38,141.45,156.43(d,J＝250.3Hz),161.04,168.05；ESI-MS calcd for C 25 H 17 F 8 N 2 O 2 ([M+H] + )529,found 529.；
n- (2-methoxy-4- (heptafluoroisopropyl-2-yl) phenyl) -2-fluoro-3- (1-oxoisoindolin-2-yl) benzamide (ZJ-12): m.p.214-216 ℃; 1 H NMR(600MHz,CDCl 3 )δ:3.95(s,3H,O-CH 3 ),4.91(s,2H,N-CH 2 ),7.10(d,J＝2.0Hz,1H,Ph-H),7.28(s,1H,Ph-H),7.42(t,J＝7.9Hz,1H,Ph-H),7.57(t,J＝7.6Hz,2H,Ph-H),7.67(td,J＝7.6,1.1Hz,1H,Ph-H),7.76(td,J＝7.7,1.8Hz,1H,Ph-H),8.00(dt,J＝7.6,1.1Hz,1H,Ph-H),8.10(ddd,J＝7.9,7.0,1.8Hz,1H,Ph-H),8.70(d,J＝8.6Hz,1H,Ph-H),9.14(d,J＝12.9Hz,1H,CONH)；ESI-MS calcd for C 25 H 17 F 8 N 2 O 3 ([M+H] + )545,found 545.；
n- (2-chloro-4- (heptafluoroisopropyl-2-yl) phenyl) -2-fluoro-3- (1-oxoisoindolin-2-yl) benzamide (ZJ-13): m.p.220-222 ℃; 1 H NMR(600MHz,CDCl 3 )δ:4.93(s,2H,N-CH 2 ),7.45(t,J＝7.9Hz,1H,Ph-H),7.56–7.59(m,3H,Ph-H),7.65–7.68(m,2H,Ph-H),7.82(td,J＝7.7,1.4Hz,1H,Ph-H),8.00(d,J＝7.8Hz,1H,Ph-H),8.15(t,J＝8.1Hz,1H,Ph-H),8.80(d,J＝8.9Hz,1H,Ph-H),9.18(d,J＝14.8Hz,1H,CONH)；ESI-MS calcd for C 24 H 14 ClF 8 N 2 O 2 ([M+H] + )549,found 549.；
n- (2, 6-dimethyl-4- (heptafluoroisopropyl-2-yl) phenyl) -2-fluoro-3- (1-oxoisoindolin-2-yl) benzamide (ZJ-14) m.p.181-183 ℃; 1 H NMR(600MHz,CDCl 3 )δ:2.37(s,6H,Ph-CH 3 ),4.91(s,2H,N-CH 2 ),7.36(s,2H,Ph-H),7.42(t,J＝7.9Hz,1H,Ph-H),7.57(t,J＝7.7Hz,2H,Ph-H),7.67(td,J＝7.5,1.1Hz,1H,Ph-H),7.72(td,J＝7.6,1.8Hz,1H,Ph-H),7.98(d,J＝7.5Hz,1H,Ph-H),8.06(t,J＝7.3Hz,1H,Ph-H),8.11(d,J＝10.2Hz,1H,CONH)；ESI-MS calcd for C 26 H 18 F 8 N 2 NaO 2 ([M+Na] + )565,found 565.；
n- (2, 5-dimethyl-4- (heptafluoroisopropyl-2-yl) phenyl) -2-fluoro-3- (1-oxoisoindolin-2-yl) benzamide (ZJ-15): m.p.196-198 ℃; 1 H NMR(600MHz,CDCl 3 )δ:2.33(s,3H,Ph-CH 3 ),2.52(d,J＝8.9Hz,3H,Ph-CH 3 ),4.90(s,2H,N-CH 2 ),7.30(s,1H,Ph-H),7.42(t,J＝7.9Hz,1H,Ph-H),7.56(t,J＝7.5Hz,2H,Ph-H),7.66(t,J＝7.5Hz,1H,Ph-H),7.73(td,J＝7.7,1.8Hz,1H,Ph-H),7.97(d,J＝7.6Hz,1H,Ph-H),8.11(t,J＝7.4Hz,1H,Ph-H),8.16(s,1H,Ph-H),8.44(d,J＝13.7Hz,1H,CONH)； 19 F NMR(564MHz,CDCl 3 )δ:-178.50(s,1F),-121.73–-121.67(m,1F),-74.71(d,J＝7.0Hz,6F)；ESI-MS calcd for C 26 H 19 F 8 N 2 O 2 ([M+H] + )543,found 543.；
n- (2-methyl-6-ethyl-4- (heptafluoroisopropyl-2-yl) phenyl) -2-fluoro-3- (1-oxoisoindolin-2-yl) benzamide (ZJ-16): m.p.233-236 ℃; 1 H NMR(600MHz,CDCl 3 )δ:1.23(t,J＝7.6Hz,3H,CH 3 CH 2 ),2.37(s,3H,Ph-CH 3 ),2.72(q,J＝7.6Hz,2H,CH 3 CH 2 ),4.92(s,2H,N-CH 2 ),7.37(s,2H,Ph-H),7.42(t,J＝7.9Hz,1H,Ph-H),7.57(t,J＝7.6Hz,2H,Ph-H),7.65–7.68(m,1H,Ph-H),7.73(td,J＝7.7,1.8Hz,1H,Ph-H),7.99(d,J＝7.5Hz,1H,Ph-H),8.04–8.09(m,2H,Ph-H,CONH).；HRMS calcd for C 27 H 21 F 8 N 2 O 2 ([M+H] + )557.1470,found 557.1471.；
n- (2-bromo-6-methyl-4- (heptafluoroisopropyl-2-yl) phenyl) -2-fluoro-3- (1-oxoisoindolin-2-yl) benzamide (ZJ-17): m.p.183-185 deg.c; 1 H NMR(600MHz,CDCl 3 )δ:2.44(s,3H,Ph-CH 3 ),4.93(s,2H,N-CH 2 ),7.43(t,J＝7.9Hz,1H,Ph-H),7.49(s,1H,Ph-H),7.57(t,J＝7.5Hz,2H,Ph-H),7.65–7.68(m,1H,Ph-H),7.74(s,1H,Ph-H),7.79(td,J＝7.7,1.8Hz,1H,Ph-H),7.99(d,J＝7.4Hz,1H,Ph-H),8.11(t,J＝7.4Hz,1H,Ph-H),8.21(d,J＝12.2Hz,1H,CONH)；ESI-MS calcd for C 25 H 16 BrF 8 N 2 O 2 ([M+H] + )607,found 607.；
n- (2-bromo-6-ethyl-4- (heptafluoroisopropyl-2-yl) phenyl) -2-fluoro-3- (1-oxoisoindolin-2-yl) benzamide (ZJ-18): m.p.204-206 ℃; 1 H NMR(600MHz,CDCl 3 )δ:1.25(t,J＝7.6Hz,3H,CH 3 CH 2 ),2.78(q,J＝7.6Hz,2H,CH 3 CH 2 ),4.92(s,2H,N-CH 2 ),7.41(t,J＝7.9Hz,1H,Ph-H),7.51(s,1H,Ph-H),7.56(t,J＝7.2Hz,2H,Ph-H),7.65(t,J＝8.0Hz,1H,Ph-H),7.74–7.77(m,2H,Ph-H),7.97(d,J＝7.3Hz,1H,Ph-H),8.06–8.09(m,1H,Ph-H),8.25(d,J＝11.3Hz,1H,CONH).；ESI-MS calcd for C 26 H 18 BrF 8 N 2 O 2 ([M+H] + )621,found 621.；
n- (2-bromo-6-methoxy-4- (heptafluoroisopropyl-2-yl) phenyl) -2-fluoro-3- (1-oxoisoindolin-2-yl) benzamide (ZJ-19): m.p.197-199 deg.C; 1 H NMR(600MHz,CDCl 3 )δ:3.90(s,3H,O-CH 3 ),4.92(s,2H,N-CH 2 ),7.11(s,1H,Ph-H),7.41(t,J＝7.9Hz,1H,Ph-H),7.50(s,1H,Ph-H),7.56(t,J＝7.8Hz,2H,Ph-H),7.66(td,J＝7.5,1.1Hz,1H,Ph-H),7.76(td,J＝7.7,1.8Hz,1H,Ph-H),7.99(dt,J＝7.5,1.0Hz,1H,Ph-H),8.06(d,J＝11.9Hz,1H,CONH),8.11(t,J＝7.3Hz,1H,Ph-H)； 19 F NMR(564MHz,CDCl 3 )δ:-181.46(s,1F),-120.47–-120.39(m,1F),-75.32(d,J＝7.3Hz,6F)；ESI-MS calcd for C25H16BrF8N2O3([M+H] + )623,found 623；ESI-MS calcd for C 25 H 16 BrF 8 N 2 O 3 ([M+H] + )623,found 623.；
n- (2-chloro-4- (heptafluoroisopropyl-2-yl) phenyl) -2-methoxy-3- (1-oxoisoindolin-2-yl) benzamide (ZJ-20): m.p.238-240 ℃; 1 H NMR(600MHz,CDCl 3 )δ:3.87(s,3H,O-CH 3 ),4.90(s,2H,N-CH 2 ),7.42(t,J＝7.9Hz,1H,Ph-H),7.56–7.59(m,3H,Ph-H),7.66–7.69(m,2H,Ph-H),7.71(dd,J＝7.8,1.8Hz,1H,Ph-H),8.00(d,J＝7.6Hz,1H,Ph-H),8.27(dd,J＝8.0,1.8Hz,1H,Ph-H),8.90(d,J＝8.9Hz,1H,Ph-H),10.78(s,1H,CONH)；HRMS calcd for C 25 H 17 ClF 7 N 2 O 3 ([M+H] + )561.0810,found 561.0806；
n- (2-bromo-4- (heptafluoroisopropyl-2-yl) phenyl) -2-methoxy-3- (1-oxoisoindolin-2-yl) benzamide (ZJ-21): m.p.206-208 ℃; 1 H NMR(600MHz,CDCl 3 )δ:3.87(s,3H,O-CH 3 ),4.90(s,2H,N-CH 2 ),7.42(t,J＝7.9Hz,1H,Ph-H),7.56–7.59(m,2H,Ph-H),7.61(d,J＝9.0Hz,1H,Ph-H),7.67(t,J＝7.5Hz,1H,Ph-H),7.71(dd,J＝7.8,1.7Hz,1H,Ph-H),7.83(d,J＝2.2Hz,1H,Ph-H),8.00(d,J＝7.5Hz,1H,Ph-H),8.26(dd,J＝7.9,1.7Hz,1H,Ph-H),8.87(d,J＝8.9Hz,1H,Ph-H),10.66(s,1H,CONH)； 13 C NMR(150MHz,CDCl 3 )δ:51.91,62.74,90.82(dq,J＝204.0,32.9Hz),113.32,120.51(qd,J＝287.9,27.6Hz,2C),121.99,122.75(d,J＝21.3Hz),123.03,124.51,125.52,126.01(d,J＝9.4Hz),126.73,128.42,129.84(d,J＝12.2Hz),131.48,131.59,131.87,132.37,134.17,139.35,141.81,154.52,162.87,168.48； 19 F NMR(564MHz,CDCl 3 )δ:-182.20–-182.13(m,1F)；-75.69(d,J＝7.0Hz,6F)；ESI-MS calcd for C 25 H 17 BrF 7 N 2 O 3 ([M+H] + )605,found 605.；
n- (2, 6-dimethyl-4- (heptafluoroisopropyl-2-yl) phenyl) -2-methoxy-3- (1-oxoisoindolin-2-yl) benzamide (ZJ-22): m.p.223-235 ℃; 1 H NMR(600MHz,CDCl 3 )δ:2.38(s,6H,Ph-CH 3 ),3.85(s,3H,O-CH 3 ),4.89(s,2H,N-CH 2 ),7.37(s,2H,Ph-H),7.40(t,J＝7.9Hz,1H,Ph-H),7.57(dt,J＝7.3,3.5Hz,2H,Ph-H),7.66–7.68(m,2H,Ph-H),8.00(d,J＝7.7Hz,1H,Ph-H),8.23(dd,J＝7.9,1.7Hz,1H,Ph-H),9.20(s,1H,CONH)； 13 C NMR(150MHz,CDCl 3 )δ19.10(2C),25.63,52.00,62.33,67.98,91.35(dq,J＝202.3,33.5Hz),120.71(qd,J＝289.1,27.5Hz,2C),123.03,124.51(2C),125.21(d,J＝20.3Hz),125.44,125.49(d,J＝10.7Hz),127.13,128.47,131.34,131.68(d,J＝12.4Hz),132.40,133.40,136.32,136.94,141.79,154.52,162.72,168.41；ESI-MS calcd for C 27 H 22 F 7 N 2 O 3 ([M+H] + )555,found 555.；
n- (2-methyl-6-ethyl-4- (heptafluoroisopropyl-2-yl) phenyl) -2-methoxy-3- (1-oxoisoindolin-2-yl) benzamide (ZJ-23): m.p.189-191 ℃; 1 H NMR(600MHz,CDCl 3 )δ:1.24(t,J＝7.6Hz,3H,CH 3 CH 2 ),2.37(s,3H,Ph-CH 3 ),2.73(q,J＝7.6Hz,2H,CH 3 CH 2 ),3.85(s,3H,O-CH 3 ),4.89(s,2H,N-CH 2 ),7.38(s,2H,Ph-H),7.41(t,J＝7.9Hz,1H,Ph-H),7.56–7.59(m,2H,Ph-H),7.66–7.69(m,2H,Ph-H),8.00(d,J＝7.7Hz,1H,Ph-H),8.24(dd,J＝7.9,1.8Hz,1H,Ph-H),9.20(s,1H,CONH)；ESI-MS calcd for C 28 H 24 F 7 N 2 O 3 ([M+H] + )569,found 569.；
n- (2-chloro-6-methyl-4- (heptafluoroisopropyl-2-yl) phenyl) -2-methoxy-3- (1-oxoisoindolin-2-yl) benzamide (ZJ-24): m.p.201-203 ℃; 1 H NMR(600MHz,CDCl 3 )δ:2.42(s,3H,Ph-CH 3 ),3.88(s,3H,O-CH 3 ),4.90(s,2H,N-CH 2 ),7.41(t,J＝7.9Hz,1H,Ph-H),7.45(s,1H,Ph-H),7.56–7.58(m,3H,Ph-H),7.67(td,J＝7.5,1.1Hz,2H,Ph-H),7.70(dd,J＝7.8,1.8Hz,1H,Ph-H),8.00(d,J＝8.0Hz,1H,Ph-H),8.23(dd,J＝7.9,1.8Hz,1H),9.59(s,1H,CONH)；ESI-MS calcd for C 26 H 19 ClF 7 N 2 O 3 ([M+H] + )575,found 575.；
n- (2-chloro-6-ethyl-4- (heptafluoroisopropyl-2-yl) phenyl) -2-methoxy-3- (1-oxoisoindolin-2-yl) benzamide (ZJ-25): 1 H NMR(600MHz,CDCl 3 )δ:1.25(t,J＝7.6Hz,3H,CH 3 CH 2 ),2.77(q,J＝7.6Hz,2H,CH 3 CH 2 ),3.88(s,3H,O-CH 3 ),4.90(s,2H,N-CH 2 ),7.41(t,J＝7.9Hz,1H,Ph-H),7.47(s,1H,Ph-H),7.55–7.58(m,2H,Ph-H),7.60(d,J＝2.1Hz,1H,Ph-H),7.67(td,J＝7.4,1.1Hz,1H,Ph-H),7.70(dd,J＝7.8,1.8Hz,1H,Ph-H),8.00(d,J＝8.1Hz,1H,Ph-H),8.24(dd,J＝7.9,1.8Hz,1H,Ph-H),9.48(s,1H,CONH)；HRMS calcd for C 27 H 21 ClF 7 N 2 O 3 ([M+H] + )589.1123,found589.1125；
n- (2-bromo-6-methyl 4- (heptafluoroisopropyl-2-yl) phenyl) -2-methoxy-3- (1-oxoisoindolin-2-yl) benzamide (ZJ-26): 1 H NMR(600MHz,CDCl 3 )δ:2.43(s,3H,Ph-CH 3 ),3.89(s,3H,O-CH 3 ),4.90(s,2H,N-CH 2 ),7.41(t,J＝7.9Hz,1H,Ph-H),7.48(s,1H,Ph-H),7.57(dt,J＝7.3,3.4Hz,2H,Ph-H),7.67(td,J＝7.5,1.1Hz,1H,Ph-H),7.70(dd,J＝7.8,1.8Hz,1H,Ph-H),7.74(d,J＝2.1Hz,1H,Ph-H),8.00(d,J＝8.1Hz,1H,Ph-H),8.24(dd,J＝7.9,1.8Hz,1H,Ph-H),9.54(s,1H,CONH)；ESI-MS calcd for C 26 H 19 BrF 7 N 2 O 3 ([M+H] + )619,found 619.；
n- (2-bromo-6-ethyl-4- (heptafluoroisopropyl-2-yl) phenyl) -2-methoxy-3- (1-oxoisoindoline-2-yl) benzamide (ZJ-27): 1 H NMR(600MHz,CDCl 3 )δ:1.25(t,J＝7.5Hz,3H,CH 3 CH 2 ),2.78(q,J＝7.6Hz,2H,CH 3 CH 2 ),3.89(s,3H,O-CH 3 ),4.89(s,2H,N-CH 2 ),7.41(t,J＝7.9Hz,1H,Ph-H),7.51(s,1H,Ph-H),7.56–7.59(m,2H,Ph-H),7.67(td,J＝7.5,1.1Hz,1H,Ph-H),7.70(dd,J＝7.8,1.8Hz,1H,Ph-H),7.76(d,J＝1.7Hz,1H,Ph-H),8.00(d,J＝8.1Hz,1H,Ph-H),8.25(dd,J＝7.9,1.8Hz,1H,Ph-H),9.46(s,1H,CONH)；ESI-MS calcd for C 27 H 21 BrF 7 N 2 O 3 ([M+H] + )633,found 633.；
n- (2, 6-dibromo-4- (heptafluoroisopropyl-2-yl) phenyl) -2-methoxy-3- (1-oxoisoindolin-2-yl) benzamide (ZJ-28): 1 H NMR(600MHz,CDCl 3 )δ:3.91(s,3H,O-CH 3 ),4.90(s,2H,N-CH 3 ),7.42(t,J＝7.9Hz,1H,Ph-H),7.57(dt,J＝7.3,3.4Hz,2H,Ph-H),7.67(td,J＝7.5,1.0Hz,1H,Ph-H),7.72(dd,J＝7.8,1.8Hz,1H,Ph-H),7.88(s,2H,Ph-H),8.00(d,J＝8.0Hz,1H,Ph-H),8.26(dd,J＝7.9,1.8Hz,1H,Ph-H),9.64(s,1H,CONH)；HRMS calcd for C 25 H 16 Br 2 F 7 N 2 O 3 ([M+H] + )682.9410,found 682.9411.；
n- (4- (heptafluoroisopropan-2-yl) phenyl) -4-methyl-3- (1-oxoisoindolin-2-yl) benzamide (ZJ-29): m.p.255-257 ℃; 1 H NMR(600MHz,CDCl 3 )δ:2.10(s,3H,Ph-CH 3 ),4.63(s,2H,N-CH 2 ),7.14(d,J＝8.0Hz,1H,Ph-H),7.39(d,J＝7.6Hz,1H,Ph-H),7.45(t,J＝7.5Hz,1H,Ph-H),7.52(d,J＝8.7Hz,2H,Ph-H),7.55(td,J＝7.5,1.0Hz,1H,Ph-H),7.78(d,J＝7.6Hz,1H,Ph-H),7.80–7.83(m,4H,Ph-H),8.98(s,1H,CONH)；ESI-MS calcd for C 25 H 18 F 7 N 2 O 2 ([M+H] + )511,found 511.；
n- (2-methyl-4- (heptafluoroisopropan-2-yl) phenyl) -4-methyl-3- (1-oxoisoindolin-2-yl) benzamide (ZJ-30): m.p.238-240 ℃; 1 H NMR(600MHz,CDCl 3 )δ:2.26(s,3H,Ph-CH 3 ),2.37(s,3H,Ph-CH 3 ),4.74(s,2H,N-CH 2 ),7.37(d,J＝8.0Hz,1H,Ph-H),7.43(s,1H,Ph-H),7.48(d,J＝7.6Hz,2H,Ph-H),7.52(t,J＝7.5Hz,1H,Ph-H),7.60(td,J＝7.5,1.1Hz,1H,Ph-H),7.78(dd,J＝7.9,1.7Hz,1H,Ph-H),7.83(d,J＝1.5Hz,1H,Ph-H),7.89(d,J＝7.6Hz,1H,Ph-H),8.06(d,J＝8.4Hz,2H,Ph-H,CONH)；ESI-MS calcd for C 26 H 20 F 7 N 2 O 2 ([M+H] + )525,found 525.；
n- (2-methoxy-4- (heptafluoroisopropan-2-yl) phenyl) -4-methyl-3- (1-oxoisoindolin-2-yl) benzamide (ZJ-31): m.p.200-201 ℃; 1 H NMR(600MHz,CDCl 3 )δ:2.35(s,3H,Ph-CH 3 ),3.97(s,3H,O-CH 3 ),4.81(s,2H,N-CH 2 ),7.10(s,1H,Ph-H),7.27(s,1H,Ph-H),7.49(d,J＝8.0Hz,1H,Ph-H),7.54–7.58(m,2H,Ph-H),7.65(t,J＝7.5Hz,1H,Ph-H),7.78(dd,J＝7.9,1.7Hz,1H,Ph-H),7.81(d,J＝1.5Hz,1H,Ph-H),7.98(d,J＝7.5Hz,1H,Ph-H),8.56(s,1H,CONH),8.64(d,J＝8.6Hz,1H,Ph-H)；ESI-MS calcd for C 26 H 20 F 7 N 2 O 3 ([M+H] + )539,found 539.；
n- (2, 6-dimethyl-4- (heptafluoroisopropan-2-yl) phenyl) -4-methyl-3- (1-oxoisoindolin-2-yl) benzamide (ZJ-32): m.p.226-228 deg.C; 1 H NMR(600MHz,CDCl 3 )δ:2.29(s,3H,Ph-CH 3 ),2.30(s,6H,Ph-CH 3 ),4.73(s,2H,N-CH 2 ),7.33(s,2H,Ph-H),7.38(d,J＝7.9Hz,1H,Ph-H),7.47(d,J＝7.6Hz,1H,Ph-H),7.53(t,J＝7.5Hz,1H,Ph-H),7.61(t,J＝7.5Hz,1H,Ph-H),7.82–7.85(m,2H),7.86(s,1H,CONH),7.91(d,J＝7.6Hz,1H,Ph-H)；ESI-MS calcd for C 27 H 22 F 7 N 2 O 2 ([M+H] + )539,found 539.；
n- (2, 5-dimethyl-4- (heptafluoroisopropan-2-yl) phenyl) -4-methyl-3- (1-oxoisoindolin-2-yl) benzamide (ZJ-33) m.p.195-197 ℃; 1 H NMR(600MHz,CDCl 3 )δ:2.28(s,3H,Ph-CH 3 ),2.30(s,3H,Ph-CH 3 ),2.50(d,J＝8.9Hz,3H,Ph-CH 3 ),4.75(s,2H,N-CH 2 ),7.28(s,1H,Ph-H),7.40(d,J＝8.0Hz,1H,Ph-H),7.49(dt,J＝7.5,0.9Hz,1H,Ph-H),7.53(t,J＝7.5Hz,1H,Ph-H),7.61(td,J＝7.5,1.2Hz,1H,Ph-H),7.77(dd,J＝7.9,1.9Hz,1H,Ph-H),7.82(d,J＝1.8Hz,1H,Ph-H),7.88(s,1H,Ph-H),7.91(dd,J＝7.6,0.9Hz,1H,Ph-H),7.94(s,1H,CONH)；ESI-MS calcd for C 27 H 22 F 7 N 2 O 2 ([M+H] + )539,found 539.；
n- (2-methyl-6-ethyl-4- (heptafluoroisopropan-2-yl) phenyl) -4-methyl-3- (1-oxoisoindolin-2-yl) benzamide (ZJ-34): m.p.183-185 deg.c; 1 H NMR(600MHz,CDCl 3 )δ:1.16(t,J＝7.6Hz,3H,CH 3 CH 2 ),2.24(s,3H,Ph-CH 3 ),2.25(s,3H,Ph-CH 3 ),2.62(q,J＝7.6Hz,2H,CH 3 CH 2 ),4.68(s,2H,N-CH 2 ),7.29(d,J＝7.9Hz,1H,Ph-H),7.42(d,J＝7.4Hz,1H,Ph-H),7.32(s,2H,Ph-H),7.51(t,J＝7.5Hz,1H,Ph-H),7.59(t,J＝7.5Hz,1H,Ph-H),7.90–7.80(m,3H),8.11(s,1H,CONH)；ESI-MS calcd for C 28 H 23 F 7 N 2 NaO 2 ([M+Na] + )575,found 575.；
n- (2-chloro-4- (heptafluoroisopropan-2-yl) phenyl) -4-methyl-3- (1-oxoisoindolin-2-yl) benzamide (ZJ-35): m.p.201-203 ℃; 1 H NMR(600MHz,CDCl 3 )δ:2.37(s,3H,Ph-CH 3 ),4.82(s,2H,N-CH 2 ),7.51(d,J＝8.0Hz,1H,Ph-H),7.60–7.54(m,3H,Ph-H),7.69–7.63(m,2H,Ph-H),7.80(dd,J＝8.0,1.7Hz,1H,Ph-H),7.86(d,J＝1.9Hz,1H,Ph-H),7.98(d,J＝7.5Hz,1H,Ph-H),8.53(s,1H,CONH),8.73(d,J＝8.9Hz,1H,Ph-H)；ESI-MS calcd for C 25 H 17 ClF 7 N 2 O 2 ([M+H] + )545,found 545.；
n- (2-bromo-4- (heptafluoroisopropan-2-yl) phenyl) -4-methyl-3- (1-oxoisoindolin-2-yl) benzamide (ZJ-36): m.p.175-177 ℃; 1 H NMR(600MHz,CDCl 3 )δ:2.37(s,3H,Ph-CH 3 ),4.82(s,2H,N-CH 2 ),7.51(d,J＝8.0Hz,1H,Ph-H),7.58–7.54(m,2H,Ph-H),7.61(d,J＝8.8Hz,1H,Ph-H),7.65(t,J＝7.4Hz,1H,Ph-H),7.80–7.83(m,2H,Ph-H),7.87(d,J＝1.5Hz,1H,Ph-H),7.98(d,J＝7.5Hz,1H,Ph-H),8.56(s,1H,CONH),8.71(d,J＝8.9Hz,1H,Ph-H)；ESI-MS calcd for C 25 H 17 BrF 7 N 2 O 2 ([M+H] + )589,found 589.；
n- (4- (heptafluoroisopropan-2-yl) phenyl) -2-fluoro-5- (1-oxoisoindolin-2-yl) benzamide (ZJ-37): m.p.209-211 ℃; 1 H NMR(600MHz,CDCl 3 )δ:4.95(s,2H,N-CH 2 ),7.29(dd,J＝11.4,9.1Hz,1H,Ph-H),7.54–7.56(m,2H,Ph-H),7.63–7.64(m,3H,Ph-H),7.85(d,J＝8.7Hz,2H,Ph-H),7.94(d,J＝7.6Hz,1H,Ph-H),8.14(dd,J＝6.5,3.0Hz,1H,Ph-H),8.67(ddd,J＝9.1,4.5,3.0Hz,1H,Ph-H),8.70(d,J＝16.2Hz,1H,CONH)；ESI-MS calcd for C 24 H 15 F 8 N 2 O 2 ([M+H] + )515,found515.；
n- (2-methyl-4- (heptafluoroisopropan-2-yl) phenyl) -2-fluoro-5- (1-oxoisoindolin-2-yl) benzamide (ZJ-38): m.p.207-208 ℃; 1 H NMR(600MHz,CDCl 3 )δ:2.45(s,3H,Ph-CH 3 ),4.97(s,2H,N-CH 2 ),7.31(dd,J＝11.6,9.1Hz,1H,Ph-H),7.48(s,1H,Ph-H),7.58–7.51(m,3H,Ph-H),7.64(td,J＝7.5,1.1Hz,1H,Ph-H),7.95(dt,J＝7.6,1.0Hz,1H,Ph-H),8.16(dd,J＝6.5,3.0Hz,1H,Ph-H),8.44(d,J＝8.7Hz,1H,Ph-H),8.65(d,J＝17.8Hz,1H,CONH),8.73(ddd,J＝9.1,4.5,3.0Hz,1H,Ph-H)；ESI-MS calcd for C 25 H 16 F 8 N 2 NaO 2 ([M+Na] + )551,found 551.；
n- (2-methoxy-4- (heptafluoroisopropan-2-yl) phenyl) -2-fluoro-5- (1-oxoisoindolin-2-yl) benzamide (ZJ-39): m.p.205-207 ℃; 1 H NMR(600MHz,CDCl 3 )δ:4.01(s,3H,O-CH 3 ),4.96(s,2H,N-CH 2 ),7.13(d,J＝2.0Hz,1H,Ph-H),7.287.31(m,2H,Ph-H),7.52–7.56(m,2H,Ph-H),7.64(td,J＝7.5,1.1Hz,1H,Ph-H),7.94(d,J＝7.6Hz,1H,Ph-H),8.13(dd,J＝6.4,3.0Hz,1H,Ph-H),8.69–8.72(m,2H),9.42(d,J＝16.3Hz,1H,CONH)；ESI-MS calcd for C 25 H 17 F 8 N 2 O 3 ([M+H] + )545,found545.；
n- (2, 6-dimethyl-4- (heptafluoroisopropan-2-yl) phenyl) -2-fluoro-5- (1-oxoisoindolin-2-yl) benzamide (ZJ-40): m.p.239-240 ℃; 1 H NMR(600MHz,CDCl 3 )δ:2.38(s,6H,Ph-CH 3 ),4.96(s,2H,N-CH 2 ),7.31(dd,J＝11.2,9.1Hz,1H,Ph-H),7.38(s,2H,Ph-H),7.52–7.56(m,2H,Ph-H),7.64(td,J＝7.5,1.2Hz,1H,Ph-H),7.94(d,J＝7.6Hz,1H,Ph-H),8.10(d,J＝15.2Hz,1H,CONH),8.12(dd,J＝6.4,3.0Hz,1H,Ph-H),8.69(ddd,J＝9.1,4.5,3.0Hz,1H,Ph-H)； 13 C NMR(150MHz,CDCl 3 )δ:18.97,50.86,91.32(dq,J＝202.2,34.1Hz),117.07,117.24,120.67(qd,J＝287.7,27.2Hz,2C),120.79(d,J＝13.1Hz),121.35(d,J＝2.2Hz),122.80,124.26,125.49,125.53,125.56,125.67,125.73,128.58,132.53,132.58,136.47,136.48,136.74(d,J＝2.2Hz),139.98,157.15(d,J＝245.2Hz),161.12(d,J＝3.9Hz),167.71； 19 F NMR(564MHz,CDCl 3 )δ:-182.27–-182.21(m,1F),-118.05–-118.02(m,1F),-75.50(d,J＝7.1Hz,6F)；ESI-MS calcd for C 26 H 19 F 8 N 2 O 2 ([M+H] + )543,found 543.；
n- (4- (heptafluoroisopropan-2-yl) phenyl) -2-chloro-5- (1-oxoisoindolin-2-yl) benzamide (ZJ-41): m.p.217-219 ℃; 1 H NMR(600MHz,DMSO-d 6 )δ:5.09(s,2H,N-CH 2 ),7.57(t,J＝7.2Hz,1H,Ph-H),7.66–7.73(m,5H,Ph-H),7.82(d,J＝7.6Hz,1H,Ph-H),8.00(d,J＝8.4Hz,2H,Ph-H),8.11(dd,J＝8.9,2.7Hz,1H,Ph-H),8.17(d,J＝2.7Hz,1H,Ph-H),11.01(s,1H,Ph-H,CONH)；ESI-MS calcd for C 24 H 15 ClF 7 N 2 O 2 ([M+H] + )531,found 531.；
n- (2-methyl-4- (heptafluoroisopropan-2-yl) phenyl) -2-chloro-5- (1-oxoisoindolin-2-yl) benzamide (ZJ-42): m.p.230-232 ℃; 1 H NMR(600MHz,CDCl 3 )δ:2.45(s,3H,Ph-CH 3 ),4.89(s,2H,N-CH 2 ),7.46–7.55(m,5H,Ph-H),7.63(td,J＝7.4,1.1Hz,1H,Ph-H),7.91(d,J＝7.5Hz,1H,Ph-H),8.14(d,J＝2.8Hz,1H,Ph-H),8.25(s,1H,CONH),8.29(dd,J＝8.9,2.7Hz,1H,Ph-H),8.34(d,J＝8.6Hz,1H,Ph-H)；ESI-MS calcd for C25H17ClF7N2O2([M+H] + )545,found 545.；
n- (2-methoxy-4- (heptafluoroisopropan-2-yl) phenyl) -2-chloro-5- (1-oxoisoindolin-2-yl) benzamide (ZJ-43): m.p.184-186 deg.C； 1 H NMR(600MHz,CDCl 3 )δ:3.96(s,3H,O-CH 3 ),4.91(s,2H,N-CH 2 ),7.12(d,J＝2.0Hz,1H,Ph-H),7.29(d,J＝8.7Hz,1H,Ph-H),7.50–7.57(m,3H,Ph-H),7.64(td,J＝7.4,1.1Hz,1H,Ph-H),7.93(dd,J＝7.5,0.9Hz,1H,Ph-H),8.08(d,J＝2.8Hz,1H,Ph-H),8.34(dd,J＝8.9,2.8Hz,1H,Ph-H),8.70(d,J＝8.6Hz,1H,Ph-H),8.89(s,1H,CONH)；ESI-MS calcd for C 25 H 17 ClF 7 N 2 O 3 ([M+H] + )561,found 561.；
N- (2, 6-dimethyl-4- (heptafluoroisopropan-2-yl) phenyl) -2-chloro-5- (1-oxoisoindolin-2-yl) benzamide (ZJ-44): m.p.241-242 ℃; 1 H NMR(600MHz,CDCl 3 )δ:2.44(s,6H,CH 3 ),4.91(s,2H,N-CH 2 ),7.38(s,2H,Ph-H),7.50–7.57(m,3H,Ph-H),7.64(td,J＝7.5,1.1Hz,1H,Ph-H),7.86(s,1H,CONH),7.92(d,J＝7.6Hz,1H,Ph-H),8.19–8.21(m,2H,Ph-H)； 13 C NMR(150MHz,CDCl 3 )δ:19.17(2C),50.53,90.59(dq,J＝203.9,33.1Hz),120.14,120.68(qd,J＝287.7,26.7Hz,2C),122.20,122.79,124.22,125.54,125.60(2C),125.73,128.64,131.06,132.36,132.71,135.02,136.23,136.63,136.65,138.63,139.82,164.32,167.84；ESI-MS calcd for C 26 H 19 ClF 7 N 2 O 2 ([M+H] + )559,found 559.；
n- (2, 5-dimethyl-4- (heptafluoroisopropan-2-yl) phenyl) -2-chloro-5- (1-oxoisoindolin-2-yl) benzamide (ZJ-45): m.p.212-214 ℃; 1 H NMR(600MHz,CDCl 3 )δ:2.38(s,3H,CH 3 ),2.54(d,J＝8.9Hz,3H,CH 3 ),4.91(s,2H,N-CH 2 ),7.32(s,1H,Ph-H),7.52–7.55(m,3H,Ph-H),7.64(t,J＝7.5Hz,1H,Ph-H),7.93(d,J＝7.5Hz,1H,Ph-H),8.14(s,1H,CONH),8.14–8.15(m,2H,Ph-H),8.32(dd,J＝7.5,1.1Hz,1H,Ph-H)；ESI-MS calcd for C 26 H 19 ClF 7 N 2 O 2 ([M+H] + )559,found 559.；
n- (2-methyl-6-ethyl-4- (heptafluoroisopropan-2-yl) phenyl) -2-chloro-5- (1-oxoisoindolin-2-yl) benzamide (ZJ-46): m.p.187-188 ℃; 1 H NMR(600MHz,CDCl 3 )δ:1.27(t,J＝7.6Hz,3H,CH 3 CH 2 ),2.44(s,3H,CH 3 ),2.79(q,J＝7.6Hz,2H CH 3 CH 2 ),4.91(s,2H,N-CH 2 ),7.39(s,2H,Ph-H),7.57–7.50(m,3H,Ph-H),7.64(td,J＝7.4,1.1Hz,1H,Ph-H),7.90(s,1H,CONH),7.92(d,J＝7.6Hz,1H,Ph-H),8.21(d,J＝18.4Hz,2H,Ph-H)； 13 C NMR(150MHz,CDCl 3 )δ14.42,19.17,25.36,50.51,91.38(dq,J＝204.7,32.2Hz),120.07,120.69(qd,J＝287.1,26.8Hz,2C),122.12,122.79,123.82(d,J＝10.7Hz),124.17,125.55,125.62,125.98(d,J＝20.4Hz),128.61,131.04,132.33,132.70,135.03,135.66,137.21,138.56,139.82,142.27,164.69,167.82；MS calcd for C 27 H 21 ClF 7 N 2 O 2 ([M+H] + )573,found 573.；
n- (2-chloro-4- (heptafluoroisopropan-2-yl) phenyl) -2-chloro-5- (1-oxoisoindolin-2-yl) benzamide (ZJ-47): m.p.204-206 ℃; 1 H NMR(600MHz,CDCl 3 )δ:4.92(s,2H),7.52–7.57(m,3H,Ph-H),7.60(d,J＝8.9Hz,1H,Ph-H),7.65(td,J＝7.6,1.0Hz,1H,Ph-H),7.69(d,J＝2.0Hz,1H,Ph-H),7.94(d,J＝7.6Hz,1H,Ph-H),8.17(d,J＝2.8Hz,1H,Ph-H),8.34(dd,J＝8.9,2.8Hz,1H,Ph-H),8.80(d,J＝8.8Hz,1H,Ph-H),8.87(s,1H,CONH)；ESI-MS calcd for C 24 H 14 Cl 2 F 7 N 2 O 2 ([M+H] + )565,found565.；
n- (2-bromo-4- (heptafluoroisopropan-2-yl) phenyl) -2-chloro-5- (1-oxoisoindolin-2-yl) benzamide (ZJ-48): m.p.176-178 ℃; 1 H NMR(600MHz,CDCl 3 )δ:4.91(s,2H,N-CH 2 ),7.53–7.56(m,3H,Ph-H),7.64(td,J＝7.4,1.1Hz,2H,Ph-H),7.85(d,J＝2.2Hz,1H,Ph-H),7.94(d,J＝7.6Hz,1H,Ph-H),8.16(d,J＝2.8Hz,1H,Ph-H),8.32(dd,J＝8.9,2.8Hz,1H,Ph-H),8.76(d,J＝8.8Hz,1H,Ph-H),8.80(s,1H,CONH)；ESI-MS calcd for C 24 H 14 BrClF 7 N 2 O 2 ([M+H] + )609,found 609.；
n- (2-bromo-6-methoxy-4- (heptafluoroisopropan-2-yl) phenyl) -2-chloro-5- (1-oxoisoindolin-2-yl) benzamide (ZJ-49): m.p.119-121 ℃; 1 H NMR(600MHz,CDCl 3 )δ:3.94(s,3H,O-CH 3 ),4.91(s,2H,N-CH 2 ),7.13(s,1H,Ph-H),7.49–7.56(m,4H,Ph-H),7.64(td,J＝7.5,1.1Hz,1H,Ph-H),7.93(d,J＝7.6Hz,1H,Ph-H),7.96(s,1H,Ph-H),8.18(s,1H,CONH),8.27(dd,J＝8.8,2.6Hz,1H,Ph-H)；ESI-MS calcd for C 25 H 16 BrClF 7 N 2 O 3 ([M+H] + )639,found 639.；
n- (4- (heptafluoroisopropan-2-yl) phenyl) -2-chloro-4-fluoro-5- (1-oxoisoindolin-2-yl) benzamide (ZJ-50): m.p.215-217 ℃; 1 H NMR(600MHz,CDCl 3 )δ:4.84(s,2H,N-CH 2 ),7.15–7.26(m,1H,Ph-H),7.48–7.53(m,2H,Ph-H),7.58(d,J＝8.0Hz,2H,Ph-H),7.63(t,J＝7.4Hz,1H,Ph-H),7.85–7.88(m,3H,Ph-H),7.98(d,J＝7.8Hz,1H,Ph-H),9.11(s,1H,CONH).；ESI-MS calcd for C 24 H 14 ClF 8 N 2 O 2 ([M+H] + )549,found 549.；
n- (2-methyl-4- (heptafluoroisopropan-2-yl) phenyl) -2-chloro-4-fluoro-5- (1-oxoisoindolin-2-yl) benzamide (ZJ-51): m.p.201-203 ℃; 1 H NMR(600MHz,CDCl 3 )δ:2.42(s,3H,CH 3 ),4.87(s,2H,N-CH 2 ),7.27(d,J＝8.4Hz,1H,Ph-H),7.46(s,1H,Ph-H),7.48–7.54(m,3H,Ph-H),7.63(t,J＝7.5Hz,1H,Ph-H),7.90(d,J＝7.6Hz,1H,Ph-H),8.14(d,J＝8.0Hz,1H,Ph-H),8.19(d,J＝8.6Hz,1H,Ph-H),8.33(s,1H,CONH)；ESI-MS calcd for C 25 H 16 ClF 8 N 2 O 2 ([M+H] + )563,found563.；
n- (2-methoxy-4- (heptafluoroisopropan-2-yl) phenyl) -2-chloro-4-fluoro-5- (1-oxoisoindolin-2-yl) benzamide (ZJ-52): m.p.162-164 ℃; 1 H NMR(600MHz,CDCl 3 )δ:3.96(s,3H,OCH 3 ),4.89(s,2H,N-CH 2 ),7.11(s,1H,Ph-H),7.28(d,J＝8.4Hz,1H,Ph-H),7.37(d,J＝10.3Hz,1H,Ph-H),7.55(t,J＝7.9Hz,2H,Ph-H),7.65(td,J＝7.5,1.1Hz,1H,Ph-H),7.96(d,J＝7.5Hz,1H,Ph-H),8.11(d,J＝8.0Hz,1H,Ph-H),8.64(d,J＝8.6Hz,1H,Ph-H),8.70(s,1H,CONH)；ESI-MS calcd for C 25 H 15 ClF 8 N 2 Na 2 O 3 ([M+Na] + )601,found 601.；
n- (2, 6-dimethyl-4- (heptafluoroisopropan-2-yl) phenyl) -2-chloro-4-fluoro-5- (1-oxoisoindolin-2-yl) benzamide (ZJ-53): m.p.208-210 ℃; 1 H NMR(600MHz,CDCl 3 )δ:2.38(s,6H,CH 3 ),4.88(s,2H,N-CH 2 ),7.30(d,J＝10.3Hz,1H,Ph-H),7.35(s,2H,Ph-H),7.51–7.53(m,2H,Ph-H),7.64(t,J＝7.4Hz,1H,Ph-H),7.86(d,J＝7.7Hz,1H),8.07(d,J＝7.9Hz,1H,Ph-H),8.24(s,1H,CONH)； 13 C NMR(150MHz,CDCl 3 )δ:19.07(2C),52.04(d,J＝5.6Hz),91.07(dq,J＝204.4,32.9Hz),119.03(d,J＝24.8Hz),120.66(qd,J＝286.6,27.7Hz,2C),122.95(2C),124.37,125.16(d,J＝11.8Hz),125.51,125.57,125.70,128.51,129.10,130.06(d,J＝10.3Hz),130.99,131.86,132.70,136.17,136.63(d,J＝2.0Hz),141.43,157.2(d,J＝257.0Hz),163.55,168.16； 19 F NMR(564MHz,CDCl 3 )δ:-182.30–-182.21(m,1F),-114.16(t,J＝9.2Hz,1F),-75.49(d,J＝7.2Hz,6F)；ESI-MS calcd for C 26 H 18 ClF 8 N 2 O 2 ([M+H] + )577,found 577.；
n- (2, 5-dimethyl-4- (heptafluoroisopropan-2-yl) phenyl) -2-chloro-4-fluoro-5- (1-oxoisoindolin-2-yl) benzamide (ZJ-54): m.p.151-153 ℃; 1 H NMR(600MHz,CDCl 3 )δ:2.36(s,3H),CH 3 ,2.52(d,J＝8.9Hz,3H,CH 3 ),4.91(s,2H,N-CH 2 ),7.31(s,1H,CONH),7.37(d,J＝10.3Hz,1H,Ph-H),7.55(t,J＝7.8Hz,2H,Ph-H),7.66(td,J＝7.5,1.2Hz,1H,Ph-H),7.95(d,J＝7.6Hz,1H,Ph-H),8.04(s,2H,Ph-H),8.15(d,J＝8.0Hz,1H,Ph-H)； 19 F NMR(564MHz,CDCl 3 )δ:-178.62–-178.49(m,1F),-113.54(t,J＝9.2Hz,1F),-74.70(d,J＝6.9Hz,6F)；ESI-MS calcd for C 26 H 18 ClF 8 N 2 O 2 ([M+H] + )577,found 577.；
n- (2-methyl-6-ethyl-4- (heptafluoroisopropan-2-yl) phenyl) -2-chloro-4-fluoro-5- (1-oxoisoindolin-2-yl) benzamide (ZJ-55): m.p.116-118 ℃; 1 H NMR(600MHz,CDCl 3 )δ:1.26(t,J＝7.6Hz,3H,CH 3 CH 2 ),2.41(s,3H,CH 3 ),2.76(q,J＝7.5Hz,2H,CH 3 CH 2 ),4.91(s,2H,N-CH 2 ),7.38–7.40(m,3H,Ph-H),7.55(t,J＝7.2Hz,2H,Ph-H),7.66(td,J＝7.4,1.2Hz,1H,Ph-H),7.95(d,J＝7.3Hz,1H,Ph-H),8.04(s,1H,CONH),8.11(d,J＝8.0Hz,1H,Ph-H)；ESI-MS calcd for C 27 H 20 ClF 8 N 2 O 2 ([M+H] + )591,found 591.。
the invention also provides a preparation method of the polyfluoroalkyl-containing isoindolinone benzamide derivative shown in the general formula A-1.
As an implementable manner, the preparation method comprises:
Figure BDA0002262135340000201
in the production method provided by the present invention, in the step of synthesizing the intermediate B-2, the catalyst used may be a catalyst suitable for the present reaction type. As a preferred mode, the catalyst is selected from boron trifluoride ethyl ether.
In the production method provided by the present invention, in the step of synthesizing intermediate B-4, the esterification reagent used may be an esterification reagent suitable for the present reaction type. In a preferred mode, the esterifying reagent is at least one selected from dialkyl sulfates and halogenated alkanes.
In the production method provided by the present invention, in the step of synthesizing the intermediate B-5, the solvent used may be a solvent suitable for the present reaction type. In a preferred embodiment, the solvent B is at least one selected from methanol, ethanol, ethyl acetate, and tetrahydrofuran.
In the preparation method provided by the invention, in the step of synthesizing the intermediate B-5, reduction reaction can be carried out in the presence of a reducing agent and a catalyst. The reducing agent may be of a type suitable for the present reaction. In a preferred embodiment, the reducing agent is at least one selected from the group consisting of iron powder and stannous chloride. The catalyst may be of a type suitable for use in the present reaction. In a preferred mode, the catalyst is at least one selected from palladium on carbon, platinum on carbon, and raney nickel.
In the preparation method provided by the invention, the base C used in the step of synthesizing the intermediate B-6 can be a base suitable for the reaction type. In a preferred embodiment, the base C is at least one selected from the group consisting of triethylamine, pyridine, potassium carbonate, sodium bicarbonate, and sodium hydride.
In the production method provided by the present invention, in the step of synthesizing the intermediate B-6, the solvent C used may be a solvent suitable for the present reaction type. In a preferred embodiment, the solvent C is at least one selected from the group consisting of N, N-dimethylformamide, methanol, ethanol, dimethyl sulfoxide, tetrahydrofuran and acetonitrile.
In the production process of the present invention, the acylating agent used in the step of synthesizing the intermediate B-8 may be an acylating agent suitable for the present reaction. In a preferred mode, the acylating agent is at least one selected from the group consisting of thionyl chloride, phosphorus trichloride, phosphorus oxychloride and phosphorus pentachloride.
In the production method provided by the present invention, in the step of synthesizing intermediate B-9, solvent D used may be a solvent suitable for the present reaction type. In a preferred embodiment, the solvent D is at least one selected from the group consisting of N, N-dimethylformamide, methanol, ethanol, dimethyl sulfoxide, tetrahydrofuran, and acetonitrile.
In the preparation method provided by the invention, in the step of synthesizing the intermediate B-9, the acid-binding agent used can be an acid-binding agent suitable for the reaction type. In a preferred embodiment, the acid scavenger is at least one selected from the group consisting of triethylamine, pyridine, potassium carbonate, sodium carbonate, and sodium bicarbonate.
The polyfluoroalkyl-containing isoindolinone benzamide derivative shown in the general formula A-1 is suitable for agricultural insecticide. As a preferred mode, the polyfluoroalkyl-containing isoindolinone benzamide derivative is used for controlling at least one pest selected from mites, lepidopteran, homopteran, hemipteran and coleopteran pests.
The invention also provides an agricultural chemical insecticide, which contains 1-99% of polyfluoroalkyl-containing isoindolinone benzamide derivative shown in the general formula A-1 in percentage by mass.
When the polyfluoroalkyl-containing isoindolinone benzamide derivative represented by the general formula A-1 of the present invention is formulated into an agricultural chemical insecticide, the agricultural chemical insecticide may further comprise carriers and adjuvants commonly used in the art, in addition to the polyfluoroalkyl-containing isoindolinone benzamide derivative represented by the general formula A-1.
When an agrochemical insecticide is formulated, the agrochemical insecticide may be formulated into various liquids, emulsifiable concentrates, suspending agents, aqueous suspensions, microemulsions, emulsions, aqueous emulsions, powders, wettable powders, soluble powders, granules, water-dispersible granules or capsules.
In formulating the agrochemical insecticide, the carrier to be added may include two kinds, and at least one of them is a surfactant. The carrier may be a solid or a liquid. Suitable solid supports include natural or synthetic clays and silicates such as: natural silica and diatomaceous earth; magnesium silicates such as talc; magnesium aluminum silicates such as kaolinite, montmorillonite and mica; white carbon black, calcium carbonate, light calcium carbonate; calcium sulfate; limestone; sodium sulfate; amine salts such as ammonium sulfate, hexamethylene diamine. Liquid carriers include water and organic solvents, which can also be used as adjuvants or antifreeze additives when water is used as a solvent or diluent. Suitable organic solvents include aromatic hydrocarbons such as: benzene, xylene, toluene, etc.; chlorinated hydrocarbons such as chlorobenzene, vinyl chloride, chloroform, dichloromethane, and the like; aliphatic hydrocarbons such as petroleum fractions, cyclohexane, light mineral oil; alcohols such as isopropyl alcohol, butyl alcohol, ethylene glycol, glycerin, cyclohexanol, and the like; and ethers and esters thereof; and also ketones, such as acetone, cyclohexanone, and dimethylformamide and N-methyl-pyrrolidone.
The surfactant may be an emulsifier, dispersant or wetting agent, and may be ionic or non-ionic. Nonionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, polyoxyethylene fatty ammonia, and commercially available emulsifiers such as: pesticide emulsion 2201B, pesticide emulsion 0203B,Farm milk 100 # Agricultural milk 500 # Agricultural milk 600 # Agricultural milk 600-2 # 1601, 2201, NP-10, NP-15 and 507 # Agricultural milk OX-635, agricultural milk OX-622, agricultural milk OX-653, agricultural milk OX-667, ningru 36 # . The dispersant comprises sodium lignosulfonate, nekal, calcium lignosulfonate, methyl naphthalene sulfonic acid formaldehyde condensate and the like. The wetting agent is: sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, etc.
The agrochemical insecticides can be prepared by a general method. For example, the active substance is mixed with a liquid solvent and/or a solid carrier, with the addition of surfactants such as emulsifiers, dispersants, stabilizers, wetting agents, and also with the addition of other auxiliaries such as: binders, defoamers, oxidizing agents, and the like.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
1. Preparation of compounds
Example 1: synthesis of intermediate 4- (heptafluoro-isopropane) -phenylamine:
9.31g (100 mmol) of aniline, 130mL of tert-butyl methyl ether and 130mL of water are added to a 500 round-bottom flask, 21.76g (125 mmol) of sodium hydrosulfite, 17.70g (175 mmol) of sodium bicarbonate and 1.70g (5 mmol) of tetrabutylammonium hydrogen sulfate are added with stirring, 36.99g (125 mmol) of heptafluoroisopropyl iodide is added dropwise, magnetic stirring is carried out at room temperature for 3h, TLC (PE: EA = 10).
The compound prepared by the test is 4- (heptafluoro-isopropyl) -aniline, and the performance data are as follows:
1 H NMR(600MHz,CDCl 3 )δ:3.94(s,2H,NH 2 ),6.72(d,J＝8.9Hz,2H,Ph-H),7.35(d,J＝8.8Hz,2H,Ph-H)； 19 F NMR(565MHz,Chloroform-d)δ:-181.72(hept,J＝7.5Hz,1F,CF(CF 3 ) 2 ),-76.08(d,J＝7.5Hz,6F,CF(CF 3 ) 2 ).
example 2: synthesis of intermediate 2-chloro-4-heptafluoro-isopropyl-aniline
4g (15.32 mmol) of the intermediate 4-2a and 20mL of acetonitrile are added into a 100mL round-bottom flask, after stirring and dissolving, 2.25g (16.85 mmol) of N-chlorosuccinimide (NCS) solid powder is added into the mixture twice, the reaction is stopped after heating and refluxing for 2h, TLC (PE: EA = 10) detects that the reaction is completed, water 30mL and ethyl acetate 60mL are added for extraction after the acetonitrile is removed by rotary evaporation, and an organic phase is dried by anhydrous magnesium sulfate after being washed by saturated common salt for three times and dried by rotary evaporation to obtain 4.1g of a red brown liquid with the yield of 97.3 percent.
The compound prepared by the test is 2-chloro-4-heptafluoro-isopropyl-aniline, and the performance data are as follows:
1H NMR(600MHz,CDCl3)δ:4.36(s,2H,NH2),6.82(d,J＝8.6Hz,1H,Ph-H),7.27(d,J＝8.6Hz,1H,Ph-H),7.47(d,J＝1.8Hz,1H,Ph-H).
example 3: synthesis of intermediate 2-chloromethylbenzoyl chloride
100.59g (750 mmol) of O-hydroxymethylbenzoic acid lactone, 70.8mL (975 mmol) of thionyl chloride, 3.42g (15 mmol) of benzyltriethylammonium chloride and 1.9mL (15 mmol) of BF3-Et2O were charged into a 500mL round-bottomed flask, and the reaction was refluxed for 8 hours with stirring, and after completion of the reaction, the excess thionyl chloride was distilled off at normal pressure and then fractionated under reduced pressure to obtain 129g of a pale yellow liquid with a yield of 91.0%.
Example 4: synthesis of intermediate methyl m-nitrobenzoate
Adding 4.5g (27 mmol) of 3-nitro-benzoic acid and 80mL of acetone into a 250mL round bottom flask, stirring to dissolve, adding 11.2g (81 mmol) of potassium carbonate, reacting to generate gas, dropwise adding 5.1g (40.5 mmol) of dimethyl sulfate at room temperature after half an hour, reacting to generate gas, reacting to become viscous, stirring for reaction for 2h, detecting by TLC (PE: EA = 5).
Through tests, the prepared compound is methyl m-nitrobenzoate, and the performance data of the compound are as follows:
m.p.78-80℃； 1 H NMR(600MHz,CDCl 3 )δ:4.00(s,3H,O-CH 3 ),7.69(t,J＝7.9Hz,1H,Ph-H)),8.38(dt,J＝7.7,1.3Hz,1H,Ph-H),8.43(ddd,J＝8.2,2.3,1.1Hz,1H,Ph-H)),8.87–8.88(m,1H,Ph-H)).
example 5: synthesis of intermediate methyl m-aminobenzoate
A1000 mL three-neck flask equipped with a mechanical stirring and reflux condenser tube is charged with 25.3g (140 mmol) of methyl 3-nitrobenzoate 4-6a and 300mL of an aqueous ethanol solution (V ethanol: V water = 5).
Through tests, the prepared compound is methyl m-aminobenzoate, and the performance data of the compound are as follows:
1H NMR(600MHz,CDCl3)δ:3.89(s,3H,O-CH3),6.86(ddd,J＝7.9,2.5,1.0Hz,1H,Ph-H),7.21(t,J＝7.8Hz,1H,Ph-H),7.35(ddd,J＝2.5,1.6,0.5Hz,1H,Ph-H),7.42(ddd,J＝7.7,1.6,1.0Hz,1H,Ph-H).
example 6: synthesis of intermediate methyl 3- (1-oxoisoindol-2-yl) benzoate
Adding 5.00g (33 mmol) of methyl 3-aminobenzoate and 50mL of tetrahydrofuran into a 250mL round-bottom flask, stirring to dissolve, adding 8.35g (83 mmol) of triethylamine, dropwise adding 6.86g (36.3 mmol) of 2- (chloromethyl) benzoyl chloride into a substrate under ice bath, slowly heating the reaction to 50 ℃ after two hours, stopping the reaction after the completion of the reaction detected by TLC (PE: EA = 3).
The compound prepared by the test is 3- (1-oxo-isoindol-2-yl) methyl benzoate, and the performance data are as follows:
m.p.166-168℃； 1 H NMR(600MHz,CDCl 3 )δ:3.94(s,3H,O-CH 3 ),4.91(s,2H,N-CH 2 ),7.49–7.54(m,3H,Ph-H),7.62(t,J＝7.5Hz,1H,Ph-H),7.85(dt,J＝7.7,1.2Hz,1H,Ph-H),7.93(d,J＝7.6Hz,1H,Ph-H),8.27–8.28(m,1H,Ph-H),8.40(ddd,J＝8.2,2.3,0.9Hz,1H,Ph-H).
example 7: synthesis of intermediate 3- (1-oxoisoindol-2-yl) benzoic acid
A500 mL flask was charged with 9.3g (34.8 mmol) of methyl 3- (1-oxoisoindol-2-yl) benzoate (4-8 a) and 60mL of tetrahydrofuran as starting materials, heated to 60 ℃ under magnetic stirring to completely dissolve the methyl, and then charged with 50mL (50 mmol) of a 1mol/L NaOH solution, heated to reflux for 1 hour, and TCL (PE: EA = 2).
The compound prepared by the test is 3- (1-oxo-isoindol-2-yl) benzoic acid, and the performance data are as follows:
m.p.275-277℃； 1 H NMR(600MHz,DMSO-d 6 )δ:5.07(s,2H,N-CH 2 ),7.55–7.59(m,2H,Ph-H),7.69(d,J＝6.9Hz,2H,Ph-H),7.77(dt,J＝7.6,1.3Hz,1H,Ph-H),7.81(d,J＝7.6Hz,1H,Ph-H),8.16(dd,J＝8.1,1.9Hz,1H,Ph-H),8.56(t,J＝1.8Hz 1H,Ph-H),13.13(s,1H,COOH)； 13 C NMR(150MHz,DMSO-d 6 )δ:50.85,120.18,123.55,123.76,123.82,125.17,128.66,129.70,131.99,132.66,132.86,140.18,141.48,167.32,167.61.
example 8: synthesis of target compound N- (2-bromo-6-methyl 4- (heptafluoroisopropyl-2-yl) phenyl) -2-methoxy-3- (1-oxoisoindolin-2-yl) benzamide (ZJ-26)
In a dry protected 50mL round bottom flask was added 0.25g 2-methoxy 3- (1-oxoisoindol-2-yl) benzoic acid and 10mL dichloromethane, slowly added dropwise with stirring 0.51g (4.00 mmol) oxalyl chloride, stirred at room temperature for 3h, evaporated to remove dichloromethane and excess oxalyl chloride, added sequentially 10mL tetrahydrofuran, 0.15g (1.5 mmol) triethylamine and 0.29g 2-bromo-6-methyl-4-heptafluoroisopropylaniline, stirred at room temperature for 3h, tcl (PE: EA = 3) to check for reaction completion, purified by column chromatography (PE: EA =4 1) after evaporation, yield 41.6% as a light yellow solid.
The compound prepared was tested as N- (2-bromo-6-methyl 4- (heptafluoroisopropyl-2-yl) phenyl) -2-methoxy-3- (1-oxoisoindolin-2-yl) benzamide with the following performance data:
m.p.194-196℃； 1 H NMR(600MHz,CDCl 3 )δ:2.43(s,3H,Ph-CH 3 ),3.89(s,3H,O-CH 3 ),4.90(s,2H,N-CH 2 ),7.41(t,J＝7.9Hz,1H,Ph-H),7.48(s,1H,Ph-H),7.57(dt,J＝7.3,3.4Hz,2H,Ph-H),7.67(td,J＝7.5,1.1Hz,1H,Ph-H),7.70(dd,J＝7.8,1.8Hz,1H,Ph-H),7.74(d,J＝2.1Hz,1H,Ph-H),8.00(d,J＝8.1Hz,1H,Ph-H),8.24(dd,J＝7.9,1.8Hz,1H,Ph-H),9.54(s,1H,CONH)；ESI-MS calcd for C 26 H 19 BrF 7 N 2 O 3 ([M+H] + )619,found 619.
2. preparation of the preparation
In the following examples 9 to 11, the components were prepared in mass percent.
Example 9, 30% suspending agent
Figure BDA0002262135340000281
The compound (ZJ-26) and other components are thoroughly mixed, and the thus-obtained suspension is diluted with water to give a diluted solution of any desired concentration.
Example 10, 30% emulsifiable concentrate
Figure BDA0002262135340000282
Dissolving phosphorous acid in toluene, adding compound (ZJ-26) and ethoxylated triglyceride to obtain transparent solution.
Example 11, 60% wettable powder
Figure BDA0002262135340000283
Figure BDA0002262135340000291
Compound (ZJ-26), sodium dodecylnaphthalenesulfonate, sodium lignosulfonate, and diatomaceous earth were mixed together and ground in a grinder until the granules met the standard.
3. Biological Activity assay
Example 12 insecticidal Activity against armyworm
And (3) fully soaking a proper amount of corn leaves in the prepared liquid medicine, naturally drying in the shade, putting the corn leaves into a culture dish filled with filter paper, inoculating 10 heads/dish of the larvae in the 3-instar middle period of the armyworm, culturing in an observation room at 24-27 ℃, and investigating the result after 48 hours. If the body of the insect is touched by a brush pen, no response is regarded as dead insect. The test concentration was 20mg/L.
The results show that the compounds ZJ-1 to ZJ-55 show a mortality of 100% at the tested concentration of 250 mg/L.
Example 13 insecticidal Activity against Plutella xylostella
The method comprises the steps of fully soaking a proper amount of cabbage leaves in prepared liquid medicine, naturally drying in the shade, putting the soaked cabbage leaves into a culture dish filled with filter paper, inoculating 10 heads/dishes of 2-instar middle-stage larvae of the diamondback moth, culturing in an observation room at 24-27 ℃, and investigating results after 48 hours. If the body of the insect is touched by a writing brush, the dead insect is determined to be no response. The test concentration was 20mg/L.
The results show that the compounds ZJ-1 to ZJ-55 show a mortality of 100% at the tested concentration of 500 mg/L.
Example 14 insecticidal Activity against Medicago Aphis
Spraying the broad bean leaf seedlings with the lucerne aphids under a Potter spray tower, culturing the lucerne aphids in an observation room at the temperature of 20-22 ℃, and investigating the result after 48 hours. If the body of the insect is touched by a brush pen, no response is regarded as dead insect. The test concentration was 200mg/L.
The results show that the compounds ZJ-1 to ZJ-55 show a mortality rate of more than 90% at the tested concentration of 500 mg/L.
Example 15 control of armyworm and Plutella xylostella by part of the Compounds at Low doses
TABLE 2
Figure BDA0002262135340000301
Figure BDA0002262135340000311
In table 2, compounds a19, B18, C18, D1, D2, E16, G21, J20, L16 are compounds disclosed in patent WO2010127928 A1. From the comparative data in table 2, it can be seen that at low concentration, 1mg/L concentration, the control effect of the compounds a19, B18, C18, D1, D2, E16, G21, J20 and L16 on armyworm and plutella xylostella is below 60%, even 0; the control effect of the compound provided by the application is more than 75%, and most of the control effect is 100%. It is thus understood that the polyfluoroalkyl-containing isoindolinone benzamide derivative represented by the general formula A-1 provided by the present application has an excellent pesticidal effect.

Claims (6)

1. Polyfluoroalkyl-containing isoindolinone benzamide derivatives have the following general formula A-1:
Figure FDA0003852826130000011
the polyfluoroalkyl-containing isoindolinone benzamide derivative shown in the general formula A-1 is selected from at least one of the following compounds:
Figure FDA0003852826130000012
2. a process for the preparation of polyfluoroalkyl group-containing isoindolinone benzamide derivatives according to claim 1, which comprises:
Figure FDA0003852826130000021
r1, R2, R3, R4 and R5 have the same meanings as defined for the corresponding radicals in claim 1.
3. The method of claim 2, wherein: the preparation method comprises the following steps:
in the synthesis of the intermediate B-2, the catalyst is selected from boron trifluoride diethyl etherate;
in the synthesis of intermediate B-4, the esterifying reagent is selected from at least one of dialkyl sulfate and halogenated alkane;
in the synthesis of the intermediate B-5, the solvent B is selected from at least one of methanol, ethanol, ethyl acetate and tetrahydrofuran, and the reduction method comprises the steps of using a reducing agent and a catalyst, wherein the reducing agent is selected from at least one of iron powder and stannous chloride, and the catalyst is selected from at least one of palladium carbon, platinum carbon and raney nickel;
when the intermediate B-6 is synthesized, the base C is selected from at least one of triethylamine, pyridine, potassium carbonate, sodium bicarbonate and sodium hydride, and the solvent C is selected from at least one of N, N-dimethylformamide, methanol, ethanol, dimethyl sulfoxide, tetrahydrofuran and acetonitrile;
when the intermediate B-8 is synthesized, the acylating agent is selected from at least one of thionyl chloride, phosphorus trichloride, phosphorus oxychloride and phosphorus pentachloride;
when the target product B-9 is synthesized, the solvent D is selected from at least one of N, N-dimethylformamide, methanol, ethanol, dimethyl sulfoxide, tetrahydrofuran and acetonitrile, and the acid-binding agent is selected from at least one of triethylamine, pyridine, potassium carbonate, sodium carbonate and sodium bicarbonate.
4. Use of a polyfluoroalkyl-containing isoindolinone benzamide derivative according to claim 1 in the preparation of an agricultural insecticide, wherein: the polyfluoroalkyl-containing isoindolinone benzamide derivative is used for agricultural pesticides.
5. Use according to claim 4, characterized in that: the polyfluoroalkyl-containing isoindolinone benzamide derivative is used for controlling at least one pest selected from mites, lepidoptera, homoptera, hemiptera and coleoptera pests.
6. An agrochemical insecticide characterized by: the agricultural chemical insecticide contains 1-99% by mass of the polyfluoroalkyl-containing isoindolinone benzamide derivative according to claim 1.
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