Summary of the invention
The object of the present invention is to provide a kind of benzamide derivatives of novel structure or its salt be agriculturally suitable for, there is following general formula (I):
Wherein:
R
1and R
2be selected from hydrogen atom, C independently of each other
1-C
6alkyl, C
1-C
6haloalkyl, C
1-C
6alkoxyl group, C
1-C
6halogenated alkoxy, halogen atom, nitro, cyano group, vinyl or ethynyl;
R
3and R
4be selected from hydrogen atom, C independently of each other
1-C
6alkyl or C
1-C
6haloalkyl;
R
5be selected from hydrogen atom, C
1-C
6alkyl, C
1-C
6haloalkyl or the phenyl replaced by 1 ~ 5 substituting group or benzyl, the substituting group in the described phenyl that replaced by 1 ~ 5 substituting group or benzyl is independently selected from hydrogen atom, halogen atom, C
1-C
6alkyl, C
1-C
6haloalkyl, C
1-C
6alkoxyl group, C
1-C
6halogenated alkoxy, C
1-C
6carbalkoxy, C
1-C
6haloalkoxycarbonyl, nitro, cyano group, vinyl or ethynyl;
X is selected from hydrogen atom, halogen atom, nitro, cyano group, C
1-C
6alkyl, C
1-C
6haloalkyl, C
1-C
6alkoxyl group or C
1-C
6halogenated alkoxy;
N is the integer of 0 ~ 4.
As preferred mode, in benzamide derivatives shown in above-mentioned general formula (I):
R
1and R
2be selected from hydrogen atom, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, n-hexyl, cyclohexyl, methoxyl group, trifluoromethoxy, oxyethyl group, positive propoxy, isopropoxy, halogen atom, nitro, cyano group, vinyl or ethynyl independently of each other;
R
3and R
4be selected from hydrogen atom, methyl, ethyl, n-propyl, 2-chloroethyl or 2-bromotrifluoromethane independently of each other;
R
5be selected from hydrogen atom, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, n-hexyl, cyclohexyl or the phenyl replaced by 1 ~ 5 substituting group or benzyl, substituting group in the described phenyl that replaced by 1 ~ 5 substituting group or benzyl is independently selected from hydrogen atom, halogen atom, methyl, ethyl, trifluoromethyl, difluoromethyl, seven fluorine sec.-propyls, methoxyl group, trifluoromethoxy, oxyethyl group, phenoxy group, methoxycarbonyl, ethoxycarbonyl, 2,2,2-trifluoroethoxy carbonyl, nitro or cyano group;
X is selected from hydrogen atom, halogen atom, nitro, cyano group, methyl, ethyl, methoxyl group, oxyethyl group, a fluorine methoxyl group, difluoro-methoxy or trifluoromethoxy;
N is the integer of 0 ~ 2.
As further preferred mode, in benzamide derivatives shown in above-mentioned general formula (I):
R
1and R
2be selected from hydrogen atom, methyl, ethyl, sec.-propyl, methoxyl group, oxyethyl group, fluorine, chlorine, bromine or iodine independently of each other;
R
3and R
4be selected from hydrogen, methyl or ethyl independently of each other;
R
5be selected from the phenyl replaced by 1 ~ 5 substituting group, substituting group in the described phenyl replaced by 1 ~ 5 substituting group is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atoms, methyl, ethyl, trifluoromethyl, difluoromethyl, seven fluorine sec.-propyls, methoxyl group, trifluoromethoxy, oxyethyl group, phenoxy group, methoxycarbonyl, ethoxycarbonyl, 2,2,2-trifluoroethoxy carbonyl, nitro or cyano group;
X is hydrogen atom;
N is 1.
Present invention also offers the preparation method of the benzamide derivatives that a kind of above-mentioned general formula (I) represents, comprise the following steps:
In general formula (II) and general formula (III), the numerical value of each substituent definition and n and optimal way are as previously mentioned.
Compound shown in compound and general formula (III) shown in general formula (II) in organic solvent, there is no alkali or under having alkali, at-10 DEG C of temperature to organic solvent boiling point used, compound shown in general formula (IV) is prepared in reaction
Shown in described general formula (II), shown in compound and general formula (III), the mol ratio of compound is 0.25 ~ 5.0:1;
Described organic solvent is selected from methylene dichloride, chloroform, tetracol phenixin, ethyl acetate, trichloromethane, ether, benzene,toluene,xylene, hexanaphthene, normal hexane, ethyl acetate, tetrahydrofuran (THF), 1, one in 4-dioxane, DMF and dimethyl sulfoxide (DMSO), more than two or three combination;
Described alkali is selected from triethylamine, pyridine, 1,8-diaza-dicyclo (5,4, O) one in undecylene-7, DMA, sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium methylate, sodium tert-butoxide and potassium tert.-butoxide, more than two or three combination;
Shown in described alkali and general formula (II), the mol ratio of compound is 0 ~ 1:1.
As preferred mode, in the preparation method of the benzamide derivatives that above-mentioned general formula (I) represents:
Shown in described general formula (II), shown in compound and general formula (III), the mol ratio of compound is 1 ~ 1.2:1;
Described organic solvent is selected from methylene dichloride and/or tetrahydrofuran (THF);
Described alkali is selected from triethylamine and/or pyridine;
Shown in described alkali and general formula (II), the mol ratio of compound is 0 ~ 0.1:1.
Compound shown in the general formula (II) that the present invention uses, can be prepared by method described in patent WO2005021488 and WO2005073165.
Benzamide derivatives described in general formula provided by the invention (I) or its salt be agriculturally suitable for, be suitable for preparing agricultural insecticide.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described, but does not limit the invention to these embodiments.One skilled in the art would recognize that all alternativess, improvement project and the equivalents that present invention encompasses and may comprise in Claims scope.
The preparation of No. 04 compound in embodiment 1 table 1
(1) preparation of N-(2,6-dimethyl-4-sevoflurane isopropyl base)-3-nitrobenzamide:
3-nitrobenzoic acid (17.75g) is dissolved in 100mL methylene dichloride, adds 13.5mL oxalyl chloride and 0.5mL DMF, room temperature reaction 2 hours.Then solvent is sloughed, dissolve with 40mL methylene dichloride, triethylamine (10.74g), 2 is added drop-wise under ice bath, in the 100mL dichloromethane solution of 6-dimethyl-4-sevoflurane isopropyl amine (30.71g), react 1 hour, then successively with 1mol/L hydrochloric acid, saturated sodium bicarbonate aqueous solution washing, anhydrous sodium sulfate drying, the mixed solvent column chromatography of sherwood oil and ethyl acetate obtains 15.50g white solid, fusing point: 191-192 DEG C.Nuclear magnetic data:
1hNMR (400Hz, CDCl
3): δ 8.76 (s, 1H), 8.46 (d, 1H), 8.30 (d, 1H), 7.74 (t, 1H), 7.67 (s, 1H), 7.38 (s, 2H), 2.34 (s, 6H).
(2) preparation of N-(2,6-dimethyl-4-sevoflurane isopropyl base)-3-AB:
N-(2,6-dimethyl-4-sevoflurane isopropyl base)-3-nitrobenzamide (2.69g) is dissolved in 50mL methyl alcohol, add palladium carbon (0.50g, palladium content 5%), normal pressure passes into hydrogen, reacts 12 hours, filter, gained filtrate desolventizing, obtains white solid 2.00g, fusing point: 174-175 DEG C.
1H NMR(400Hz,CDCl
3):δ7.35-7.20(m,6H),6.88(dd,1H),3.84(br s,2H),2.34(s,6H).
(3) N-(2,6-dimethyl-4-sevoflurane isopropyl base)-3-(3-phenylurea) benzamide (compound 04):
N-(2,6-dimethyl-4-sevoflurane isopropyl base)-3-AB (0.147g) is dissolved in 5mL methylene dichloride, adds the triethylamine of catalytic amount, add phenylisocyanate, then stirring at room temperature 3 hours, separates out white solid.Filter, a small amount of washed with dichloromethane filter cake obtains 0.130g white solid, fusing point: 274 DEG C.
According to the preparation method of embodiment 1, derivative 01-90 described in the table 1 adopting different raw materials to prepare, partial derivatives nucleus magnetic hydrogen spectrum data list table 2 in.
Table 1 (R
3, R
4, R
6, X is hydrogen atom)
Sequence number |
R
1 |
R
2 |
R
5 |
Fusing point (DEG C) |
01 |
CH
3 |
CH
3 |
4-chloro-phenyl- |
290 |
02 |
CH
3 |
CH
3 |
3-trifluoromethyl-4-fluorophenyl |
253-255 |
03 |
CH
3 |
CH
3 |
2,4,6-trichlorophenyl |
309-311 |
04 |
CH
3 |
CH
3 |
Phenyl |
274 |
05 |
CH
3 |
CH
3 |
3,4-dichlorophenyl |
230-231 |
06 |
CH
3 |
CH
3 |
2-trifluoromethyl-3-aminomethyl phenyl |
283-285 |
07 |
CH
3 |
CH
3 |
4-nitrophenyl |
288-289 |
08 |
CH
3 |
CH
3 |
4-ethoxyl phenenyl |
257-258 |
09 |
CH
3 |
CH
3 |
2,3-dichlorophenyl |
305-306 |
10 |
CH
3 |
CH
3 |
3-aminomethyl phenyl |
257-258 |
11 |
CH
3 |
CH
3 |
2-chloro-phenyl- |
272-275 |
12 |
CH
3 |
CH
3 |
3-chloro-2-methyl phenyl |
270-271 |
13 |
CH
3 |
CH
3 |
2-p-methoxy-phenyl |
188-189 |
14 |
CH
3 |
CH
3 |
2-aminomethyl phenyl |
275-276 |
15 |
CH
3 |
CH
3 |
4-nitro-2-aminomethyl phenyl |
245 |
16 |
CH
3 |
CH
3 |
2,4 dichloro benzene base |
273-274 |
17 |
CH
3 |
CH
3 |
4-(2,2,2-trifluoro ethoxy carbonyl) phenyl |
243-245 |
18 |
CH
3 |
CH
3 |
2-fluorophenyl |
255-256 |
19 |
CH
3 |
CH
3 |
3,4-3,5-dimethylphenyl |
274-275 |
20 |
CH
3 |
CH
3 |
3,5-difluorophenyl |
272-273 |
21 |
CH
3 |
CH
3 |
3-Trifluoromethoxyphen-l |
259-260 |
22 |
CH
3 |
CH
3 |
3,4-difluorophenyl |
279-280 |
23 |
CH
3 |
CH
3 |
4-sevoflurane isopropyl base |
269-270 |
24 |
CH
3 |
CH
3 |
4-Phenoxyphenyl |
260-261 |
25 |
CH
3 |
CH
3 |
3-difluoro-methoxy phenyl |
246-247 |
26 |
CH
3 |
CH
3 |
2-Trifluoromethoxyphen-l |
266-268 |
27 |
CH
3 |
CH
3 |
3-nitrophenyl |
297-298 |
28 |
CH
3 |
CH
3 |
2-cyano-phenyl |
197-198 |
29 |
CH
3 |
CH
3 |
The bromo-2-cyano-phenyl of 4- |
230-233 |
30 |
CH
3 |
CH
3 |
3-chloro-phenyl- |
298-299 |
31 |
CH
3 |
CH
3 |
The chloro-2-cyano-phenyl of 4- |
263-265 |
32 |
CH
3 |
CH
3 |
2,6-diethyl phenyl |
275-276 |
33 |
CH
3 |
CH
3 |
2,4 difluorobenzene base |
183-185 |
34 |
CH
3 |
CH
3 |
2,5-3,5-dimethylphenyl |
266-268 |
35 |
CH
3 |
CH
3 |
4-aminomethyl phenyl |
280-281 |
36 |
CH
3 |
CH
3 |
2,4-3,5-dimethylphenyl |
266-267 |
37 |
CH
3 |
CH
3 |
4-tert-butyl-phenyl |
278-279 |
38 |
CH
3 |
CH
3 |
3-fluorophenyl |
259-260 |
39 |
CH
3 |
CH
3 |
2-fluorophenyl |
255-256 |
40 |
CH
3 |
CH
3 |
2,6-3,5-dimethylphenyl |
283 |
41 |
CH
3 |
CH
3 |
2,3,4-trifluorophenyl |
262-263 |
42 |
CH
3 |
CH
3 |
2,3-3,5-dimethylphenyl |
274-275 |
43 |
CH
3 |
CH
3 |
3-trifluoromethyl |
256 |
44 |
CH
3 |
CH
3CH
2 |
2,3-3,5-dimethylphenyl |
250-251 |
45 |
CH
3 |
CH
3CH
2 |
3-difluoro-methoxy phenyl |
228-229 |
46 |
CH
3 |
CH
3CH
2 |
2,4 dichloro benzene base |
236-237 |
47 |
CH
3 |
CH
3CH
2 |
2-aminomethyl phenyl |
263 |
48 |
CH
3 |
CH
3CH
2 |
4-Trifluoromethoxyphen-l |
224-225 |
49 |
CH
3 |
CH
3CH
2 |
4-(2,2,2-trifluoro ethoxy carbonyl) phenyl |
215 |
50 |
CH
3 |
CH
3CH
2 |
2-fluorophenyl |
252-253 |
51 |
CH
3 |
CH
3CH
2 |
3,4-difluorophenyl |
193-194 |
52 |
CH
3 |
CH
3CH
2 |
2-chloro-phenyl- |
248-249 |
53 |
CH
3 |
CH
3CH
2 |
3-aminomethyl phenyl |
262-263 |
54 |
CH
3 |
CH
3CH
2 |
2-p-methoxy-phenyl |
205-206 |
55 |
CH
3 |
CH
3CH
2 |
3-chloro-2-methyl phenyl |
272-273 |
56 |
CH
3 |
CH
3CH
2 |
4-nitro-2-aminomethyl phenyl |
228-229 |
57 |
CH
3 |
CH
3CH
2 |
2,3,4-trifluorophenyl |
182 |
58 |
CH
3 |
CH
3CH
2 |
4-trifluoromethoxy |
168-169 |
59 |
CH
3 |
CH
3CH
2 |
4-aminomethyl phenyl |
262-263 |
60 |
CH
3 |
CH
3CH
2 |
3,4-3,5-dimethylphenyl |
259-260 |
61 |
CH
3 |
CH
3CH
2 |
4-sevoflurane isopropyl base |
250 |
62 |
CH
3 |
CH
3CH
2 |
3-trifluoromethyl |
269-270 |
63 |
CH
3 |
CH
3CH
2 |
3-Trifluoromethoxyphen-l |
253-254 |
64 |
CH
3 |
CH
3CH
2 |
2,5-3,5-dimethylphenyl |
257-258 |
65 |
CH
3 |
CH
3CH
2 |
3,4-difluorophenyl |
260-261 |
66 |
CH
3 |
CH
3CH
2 |
3-fluorophenyl |
265-266 |
67 |
CH
3 |
CH
3CH
2 |
4-tert-butyl-phenyl |
273-274 |
68 |
CH
3 |
CH
3CH
2 |
4-Phenoxyphenyl |
228-229 |
69 |
CH
3 |
CH
3CH
2 |
2,4 difluorobenzene base |
194-195 |
70 |
CH
3 |
CH
3CH
2 |
2,4-3,5-dimethylphenyl |
266-267 |
71 |
CH
3 |
CH
3CH
2 |
2,6-diethyl phenyl |
268-269 |
72 |
CH
3 |
CH
3CH
2 |
2,6-3,5-dimethylphenyl |
272-273 |
73 |
CH
3 |
CH
3CH
2 |
3,5-3,5-dimethylphenyl |
273-274 |
74 |
CH
3 |
CH
3CH
2 |
3-nitrophenyl |
266-267 |
75 |
CH
3 |
CH
3CH
2 |
3-trifluoromethyl-2-aminomethyl phenyl |
277-278 |
76 |
CH
3 |
CH
3CH
2 |
Phenyl |
269-270 |
77 |
CH
3 |
CH
3CH
2 |
2-cyano-phenyl |
212-213 |
78 |
CH
3 |
CH
3CH
2 |
4-chloro-phenyl- |
254-255 |
79 |
CH
3 |
CH
3CH
2 |
3,4-dichlorophenyl |
284-285 |
80 |
CH
3 |
CH
3CH
2 |
2,3-dichlorophenyl |
134-135 |
81 |
CH
3 |
CH
3CH
2 |
The chloro-2-cyano-phenyl of 4- |
213-214 |
82 |
CH
3 |
CH
3CH
2 |
2,3,5-trifluorophenyl |
274-275 |
83 |
CH
3 |
CH
3CH
2 |
The chloro-5-trifluoromethyl of 4- |
140-141 |
84 |
CH
3 |
CH
3CH
2 |
The bromo-2-cyano-phenyl of 4- |
233-234 |
85 |
CH
3 |
CH
3CH
2 |
3-chloro-phenyl- |
280-281 |
86 |
CH
3 |
CH
3CH
2 |
Phenyl |
128-129 |
87 |
CH
3 |
CH
3CH
2 |
5-trifluoromethyl-2-fluorophenyl |
243 |
88 |
CH
3 |
CH
3CH
2 |
2,6-dichlor-4-trifluoromethyl phenyl |
174-175 |
89 |
CH
3 |
CH
3CH
2 |
4-nitrophenyl |
287-288 |
90 |
CH
3 |
CH
3CH
2 |
4-methoxycarbonyl phenyl |
233-235 |
Table 2
Embodiment 2
Provide below and use compound provided by the invention to test, verify insect evaluated biological activity, it is to be noted that the present invention is not only confined in the scope of following example.
Derivative (01 ~ 90) in table 1 provided by the invention is dissolved in solvent, water and tensio-active agent respectively, is mixed into homogeneous aqueous phase, during use, is diluted with water to the solution of different concns, tested object and testing method as follows:
Evaluated biological activity to oriental armyworm: supply examination insect to be oriental armyworm (Mythimna separata Walker), the normal population that indoor leaf of Semen Maydis is raised.Adopt leaf dipping method, dipping Maize Seedling leaf, in the solution configured, puts into culture dish after drying, access 3 mid-term in age larva, each concentration repeats 4 times; Contrast acetone soln soaking maize leaf breeding grub; Viewing test result after 24 hours, 48 hours, 72 hours.Completely dead with armyworm larvae, namely with the motionless death standard for larva that writing brush touches.
Test statistics: add up the dead borer population of each process and borer population of living, calculate mortality ratio:
Mortality ratio (%)=[(borer population of living after examination borer population-medicine) ÷ tries borer population] × 100
Under 500mg/L concentration, the mortality ratio of compound 50,54,57,58,69,77,80,83,85,87,90 pairs of mythimna separatas is more than or equal to 70%.