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CN1194975C - Helerocyclic substituted benzoxazine cyclic compound having biological activity - Google Patents

Helerocyclic substituted benzoxazine cyclic compound having biological activity Download PDF

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Publication number
CN1194975C
CN1194975C CNB031182267A CN03118226A CN1194975C CN 1194975 C CN1194975 C CN 1194975C CN B031182267 A CNB031182267 A CN B031182267A CN 03118226 A CN03118226 A CN 03118226A CN 1194975 C CN1194975 C CN 1194975C
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chf
och
compounds
het
ch2c
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CN1442416A (en
Inventor
侯仲轲
任叶果
黄明智
雷满香
欧晓明
臧开保
王晓光
柳爱平
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Hunan Research Institute of Chemical Industry
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Hunan Research Institute of Chemical Industry
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Priority to AU2003304029A priority patent/AU2003304029A1/en
Priority to PCT/CN2003/000501 priority patent/WO2004087694A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Secondary Cells (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention discloses heterocycle substituted benzoxazine cyclic compounds shown in a general formula (I) and a preparation process thereof, wherein the Het of the formula (I) is Y=0, S; W=0, 1; X is F, Cl, CH3, CF3 or CN; R2 is H, CH3 or Ph; R is F, Cl, Br, CH3 or NO2; m represents the number of substituents and can be 0, 1, 2, 3 or 4; When Het=(II), R1 is CH3, CHF2, CH2CH3, CH2CN, CH2CH2CH3, CH2CH=CH2, CH2C(triple bond)CH CH2C(triple bond)C-Br, CH2C(triple bond)C-Cl, CH2C(triple bond)C-I or CH2OCH2CH3; when Het= (III) R1 is only CH2C(triple bond)C-I. The compounds of the present invention has outstanding herbicidal activity, a part of the compounds has the preventing effect higher than or equal to 90 percent for most of latifoliate weeds when the compounds are used in the low dose of 18.75 ga. i/ha, and the compounds are safe to the crops of grain sorghum, maize, paddy rice, soybean, etc.

Description

A kind of heterocyclic substituted benzo oxazine lopps compound of biologically active
Technical field: the benzoxazine lopps compound and preparation method thereof that the present invention relates to a kind of heterocyclic substituted of biologically active.
Background technology: according to the literature 1,2,4,5-four substituted benzene compounds are a kind of proporphyrinogen oxidase inhibitors, have weeding activity.Wherein fused heterocycle four substituted benzene compounds have more biological activity, existing many abroad patent reports.For example: EP420194, US4640707, USP5084084, USP5127935, USP5322835, USP6323154, DE3922107, JP03,47180, USP5232898, JP62277383, EP362615 etc. have reported a lot of fused heterocycle four substituted benzene compounds and compound preparation has weeding activity.Wherein compound (flumioxazin) commercialization.
Patent US5696056, JP2001-328911 report that following structural compounds and preparation thereof also have weeding activity in addition.
Figure C0311822600042
Above-mentioned various replacement fused heterocyclic derivative all has weeding activity in various degree, but the selective herbicidal effect to broadleaved herb is relatively poor, when being used for paddy rice, wheat, corn, Soybean and Other Crops weeding, cauline leaf processing meeting damages crop itself behind the bud, only be applicable to the preceding soil treatment of bud of crop, relatively poor to weeds preventive effect in vegetative period.
Summary of the invention: the purpose of this invention is to provide benzoxazine lopps compound and preparation method thereof with the heterocyclic substituted of the biologically active of general structure (I) expression, prior characteristics are to be applicable to the bud aftertreatment, to paddy rice, jowar, soybean, seeding corn and other crops safety.(I) is as follows for general structure of the present invention:
Figure C0311822600043
Het is in the formula (1):
Figure C0311822600051
Y=O, S; Better be O;
W=0,1; Better be 1;
X is F, Cl, CH 3, CF 3, CN; It better is fluorine;
R 2Be H, CH 3, Ph; Better be H;
R is F, Cl, Br, CH 3, NO 2It better is fluorine;
M represents substituent number optional 0,1,2,3,4; Better be 0;
When Het=(II), R 1Be CH 3, CHF 2, CH 2CH 3, CH 2CN, CH 2CH 2CH 3, CH 2CH=CH 2, CH 2C ≡ CH, CH 2C ≡ C-Br, CH 2C ≡ C-Cl, CH 2C ≡ C-I, CH 2OCH 2CH 3Better be proyl, iodine proyl;
When Het=(III), R 1Only be CH 2C ≡ C-I;
The preparation method of formula of of the present invention (I) compound is as follows:
Figure C0311822600052
W in the formula, X, Y, R, R 1, R 2, m defines with claim 1;
Intermediate (A) adds corresponding (hydrogenation) phthalic anhydride (B) that replaces in appropriate solvent, be heated to 30～150 ℃, and stirring reaction obtained (C) in 1～12 hour.Solvent is a glacial acetic acid preferably; Mol ratio is 1: 1.2 preferably; Preferable temperature is the solvent refluxing temperature; The more excellent reaction times is 3 hours.
Compound (C) adds acid binding agent in appropriate solvent and halide reaction obtains target general formula (I) compound.Wherein solvent is DMF preferably; Acid binding agent is NaH preferably; Mol ratio is (C) preferably: halogenide: NaH=1: 1: 1.2; 25 ℃ of preferable temperature; 8 hours more excellent reaction times.
Synthesized reference document US 4734124 methods of intermediate (A) are as follows:
Figure C0311822600061
Raw material (D) adds ethyl bromoacetate and acid binding agent in appropriate solvent, be heated to 30～150 ℃, and stirring reaction obtained (E) in 1～12 hour.Wherein solvent is an acetone preferably; Acid binding agent is K preferably 2CO 3Mol ratio is raw material (D) preferably: ethyl bromoacetate: acid binding agent=1: 1: 1.5; Preferable temperature is the solvent refluxing temperature; The more excellent reaction times is 3 hours.
Compound (E) joins in the appropriate solvent that contains reduced iron powder, is heated to 30 ℃～120 ℃, and stirring reaction obtained (F) in 1 hour～12 hours.Wherein solvent is a glacial acetic acid preferably; Mol ratio is raw material (E) preferably: reduced iron powder=1: 5; Preferable temperature is 80 ℃; The more excellent reaction times is 3 hours.
Compound (F) joins in 80% sulfuric acid, is cooled to 0 ℃, drips 60% nitric acid, and the nitration reaction certain hour obtains (G), and it obtains intermediate (A) with the reduced iron powder reduction in glacial acetic acid.
According to above-mentioned preparation method, synthesized the benzoxazine lopps compound of a series of heterocyclic substituted of the present invention, specifically see the following form.
Figure C0311822600062
(seeing Table 1) (seeing Table 2)
Table 1:
NO W Y X R 2 R 1 R m
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CH 2CN CH 2CN CH 2CN CH 2CN CH 2CN CH 2CN CH 2CN CH 2CN 3-Cl 3-Br 3-F 3-CH 3 3-NO 2 4-F 4-Cl 4-Br 4-CH 3 4-NO 2 3，6-2Cl 3，6-2F 4，5-2Cl 3，4，5，6，-4Cl 3，4，5，6，-4F 3，4，5，6，-4Br - 3-Cl 3-Br 3-F 3-CH 3 3-NO 2 4-F 4-Cl 4-Br 4-CH 3 4-NO 2 3，6-2Cl 3，6-2F 4，5-2Cl 3，4，5，6，-4Cl 3，4，5，6，-4F 3，4，5，6，-4Br - 3-Cl 3-Br 3-F 3-CH 3 3-NO 2 4-F 4-Cl
NO W Y X R 2 R 1 R m
43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H CH 2CN CH 2CN CH 2CN CH 2CN CH 2CN CH 2CN CH 2CN CH 2CN CH 2CN CH 2CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 4-Br 4-CH 3 4-NO 2 3，6-2Cl 3，6-2F 4，5-2Cl 3，4，5，6，-4Cl 3，4，5，6，-4F 3，4，5，6，-4Br - 3-Cl 3-Br 3-F 3-CH 3 3-NO 2 4-F 4-Cl 4-Br 4-CH 3 4-NO 2 3，6-2Cl 3，6-2F 4，5-2Cl 3，4，5，6，-4Cl 3，4，5，6，-4F 3，4，5，6，-4Br - 3-Cl 3-Br 3-F 3-CH 3 3-NO 2 4-F 4-Cl 4-Br 4-CH 3 4-NO 2 3，6-2Cl 3，6-2F 4，5-2Cl 3，4，5，6，-4Cl 3，4，5，6，-4F
NO W Y X R 2 R 1 R m
85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H CH 2CH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH 3，4，5，6，-4Br - 3-Cl 3-Br 3-F 3-CH 3 3-NO 2 4-F 4-Cl 4-Br 4-CH 3 4-NO 2 3，6-2Cl 3，6-2F 4，5-2Cl 3，4，5，6，-4Cl 3，4，5，6，-4F 3，4，5，6，-4Br - 3-Cl 3-Br 3-F 3-CH 3 3-NO 2 4-F 4-Cl 4-Br 4-CH 3 4-NO 2 3，6-2Cl 3，6-2F 4，5-2Cl 3，4，5，6，-4Cl 3，4，5，6，-4F 3，4，5，6，-4Br - 3-Cl 3-Br 3-F 3-CH 3 3-NO 2 4-F
NO W Y X R 2 R 1 R M
127 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 153 154 155 156 157 158 159 160 161 162 163 164 165 166 167 168 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl 4-Cl 4-Br 4-CH 3 4-NO 2 3，6-2Cl 3，6-2F 4，5-2Cl 3，4，5，6，-4Cl 3，4，5，6，-4F 3，4，5，6，-4Br - 3-Cl 3-Br 3-F 3-CH 3 3-NO 2 4-F 4-Cl 4-Br 4-CH 3 4-NO 2 3，6-2Cl 3，6-2F 4，5-2Cl 3，4，5，6，-4Cl 3，4，5，6，-4F 3，4，5，6，-4Br - 3-Cl 3-Br 3-F 3-CH 3 3-NO 2 4-F 4-Cl 4-Br 4-CH 3 4-NO 2 3，6-2Cl 3，6-2F 4，5-2Cl 3，4，5，6，-4Cl
169 170 171 172 173 174 175 176 177 178 179 180 181 182 183 184 185 186 187 188 189 190 191 192 193 194 195 196 197 198 199 200 201 202 203 204 205 206 207 208 209 210 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F H H H H H H H H H H H H H H H H H H H CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 3，4，5，6，-4F 3，4，5，6，-4Br - 3-Cl 3-Br 3-F 3-CH 3 3-NO 2 4-F 4-Cl 4-Br 4-CH 3 4-NO 2 3，6-2Cl 3，6-2F 4，5-2Cl 3，4，5，6，-4Cl 3，4，5，6，-4F 3，4，5，6，-4Br - 3-Cl 3-Br 3-F 3-CH 3 3-NO 2 4-F 4-Cl 4-Br 4-CH 3 4-NO 2 3，6-2Cl 3，6-2F 4，5-2Cl 3，4，5，6，-4Cl 3，4，5，6，-4F 3，4，5，6，-4Br - 3-Cl 3-Br 3-F 3-CH 3 3-NO 2
NO W Y X R 2 R 1 R m
212 212 213 214 215 216 217 218 219 220 221 222 223 224 225 226 227 228 229 230 231 232 233 234 235 236 237 238 239 240 241 242 243 244 245 246 247 248 249 250 251 252 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CHF 2 CH 2CN CH 2CN CH 2CN CH 2CN CH 2CN CH 2CN CH 2CN CH 2CN CH 2CN CH 2CN CH 2CN CH 2CN CH 2CN CH 2CN CH 2CN CH 2CN CH 2CN CH 2CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 3 4-F 4-Cl 4-Br 4-CH 3 4-NO 2 3，6-2Cl 3，6-2F 4，5-2Cl 3，4，5，6，-4Cl 3，4，5，6，-4F 3，4，5，6，-4Br - 3-Cl 3-Br 3-F 3-CH 3 3-NO 2 4-F 4-Cl 4-Br 4-CH 3 4-NO 2 3，6-2Cl 3，6-2F 4，5-2Cl 3，4，5，6，-4Cl 3，4，5，6，-4F 3，4，5，6，-4Br - 3-Cl 3-Br 3-F 3-CH 3 3-NO 2 4-F 4-Cl 4-Br 4-CH 3 4-NO 2 3，6-2Cl 3，6-2F 4，5-2Cl
NO W Y X R 2 R 1 R m
253 254 255 256 257 258 259 260 261 262 263 264 265 266 267 268 269 270 271 272 273 274 275 276 277 278 279 280 281 282 283 284 285 286 287 288 289 290 291 292 293 294 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2CH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2OCH 2CH 3 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 3，4，5，6，-4Cl 3，4，5，6，-4F 3，4，5，6，-4Br - 3-Cl 3-Br 3-F 3-CH 3 3-NO 2 4-F 4-Cl 4-Br 4-CH 3 4-NO 2 3，6-2Cl 3，6-2F 4，5-2Cl 3，4，5，6，-4Cl 3，4，5，6，-4F 3，4，5，6，-4Br - 3-Cl 3-Br 3-F 3-CH 3 3-NO 2 4-F 4-Cl 4-Br 4-CH 3 4-NO 2 3，6-2Cl 3，6-2F 4，5-2Cl 3，4，5，6，-4Cl 3，4，5，6，-4F 3，4，5，6，-4Br - 3-Cl 3-Br 3-F 3-CH 3
NO W Y X R 2 R 1 R m
295 296 297 298 299 300 301 302 303 304 305 306 307 308 309 400 401 402 403 404 405 406 407 408 409 410 411 412 413 414 415 416 417 418 419 420 421 422 423 424 425 426 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2CH＝CH 2 CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡CH CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I 3-NO 2 4-F 4-Cl 4-Br 4-CH 3 4-NO 2 3，6-2Cl 3，6-2F 4，5-2Cl 3，4，5，6，-4Cl 3，4，5，6，-4F 3，4，5，6，-4Br - 3-Cl 3-Br 3-F 3-CH 3 3-NO 2 4-F 4-Cl 4-Br 4-CH 3 4-NO 2 3，6-2Cl 3，6-2F 4，5-2Cl 3，4，5，6，-4Cl 3，4，5，6，-4F 3，4，5，6，-4Br - 3-Cl 3-Br 3-F 3-CH 3 3-NO 2 4-F 4-Cl 4-Br 4-CH 3 4-NO 2 3，6-2Cl 3，6-2F
NO W Y X R 2 R 1 R m
427 428 429 430 431 432 433 434 435 436 437 438 439 440 441 442 443 444 445 446 447 448 449 450 451 452 453 454 455 456 457 458 459 460 461 462 463 464 465 466 467 468 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 Ph Ph Ph Ph CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Cl CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2C≡C-Br CH 2CH 2CH 3 CH 2C≡CH CH 2OCH 2CH 3 CH 2C≡C-I 4，5-2Cl 3，4，5，6，-4Cl 3，4，5，6，-4F 3，4，5，6，-4Br - 3-Cl 3-Br 3-F 3-CH 3 3-NO 2 4-F 4-Cl 4-Br 4-CH 3 4-NO 2 3，6-2Cl 3，6-2F 4，5-2Cl 3，4，5，6，-4Cl 3，4，5，6，-4F 3，4，5，6，-4Br - 3-Cl 3-Br 3-F 3-CH 3 3-NO 2 4-F 4-Cl 4-Br 4-CH 3 4-NO 2 3，6-2Cl 3，6-2F 4，5-2Cl 3，4，5，6，-4Cl 3，4，5，6，-4F 3，4，5，6，-4Br - - - -
NO W Y X R 2 R 1 R m
469 470 471 472 473 474 475 476 477 478 479 480 481 482 483 484 485 486 487 488 489 490 491 492 493 494 495 496 497 498 499 500 501 502 503 504 505 506 507 508 509 510 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H CH 3 CHF 2 CH 2CN CH 2CH 3 CH 2CH 2CH 3 CH 2OCH 2CH 3 CH 2CH＝CH 2 CH 2C≡CH CH 2C≡C-I CH 2C≡C-Cl CH 2C≡C-Br CH 3 CHF 2 CH 2CN CH 2CH 3 CH 2CH 2CH 3 CH 2OCH 2CH 3 CH 2CH＝CH 2 CH 2C≡CH CH 2C≡C-I CH 2C≡C-Cl CH 2C≡C-Br CH 3 CHF 2 CH 2CN CH 2CH 3 CH 2CH 2CH 3 CH 2OCH 2CH 3 CH 2CH＝CH 2 CH 2C≡CH CH 2C≡C-I CH 2C≡C-Cl CH 2C≡C-Br CH 3 CHF 2 CH 2CN CH 2CH 3 CH 2CH 2CH 3 CH 2OCH 2CH 3 CH 2CH＝CH 2 CH 2C≡CH CH 2C≡C-I - - - - - - - - - - - 3-F 3-F 3-F 3-F 3-F 3-F 3-F 3-F 3-F 3-F 3-F 4-F 4-F 4-F 4-F 4-F 4-F 4-F 4-F 4-F 4-F 4-F 3，4，5，6，-4F 3，4，5，6，-4F 3，4，5，6，-4F 3，4，5，6，-4F 3，4，5，6，-4F 3，4，5，6，-4F 3，4，5，6，-4F 3，4，5，6，-4F 3，4，5，6，-4F
NO W Y X R 2 R 1 R m
511 512 513 514 515 516 517 518 519 520 521 522 523 524 525 526 527 528 529 530 531 532 533 534 535 536 537 538 539 540 541 542 543 544 545 546 547 548 549 550 551 552 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl H H CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 2C≡C-Cl CH 2C≡C-Br CH 3 CHF 2 CH 2CN CH 2CH 3 CH 2CH 2CH 3 CH 2OCH 2CH 3 CH 2CH＝CH 2 CH 2C≡CH CH 2C≡C-I CH 2C≡C-Cl CH 2C≡C-Br CH 3 CHF 2 CH 2CN CH 2CH 3 CH 2CH 2CH 3 CH 2OCH 2CH 3 CH 2CH＝CH 2 CH 2C≡CH CH 2C≡C-I CH 2C≡C-Cl CH 2C≡C-Br CH 3 CHF 2 CH 2CN CH 2CH 3 CH 2CH 2CH 3 CH 2OCH 2CH 3 CH 2CH＝CH 2 CH 2C≡CH CH 2C≡C-I CH 2C≡C-Cl CH 2C≡C-Br CH 3 CHF 2 CH 2CN CH 2CH 3 CH 2CH 2CH 3 CH 2OCH 2CH 3 CH 2CH＝CH 2 3，4，5，6，-4F 3，4，5，6，-4F - - - - - - - - - - - 3-F 3-F 3-F 3-F 3-F 3-F 3-F 3-F 3-F 3-F 3-F 4-F 4-F 4-F 4-F 4-F 4-F 4-F 4-F 4-F 4-F 4-F 3，4，5，6，-4F 3，4，5，6，-4F 3，4，5，6，-4F 3，4，5，6，-4F 3，4，5，6，-4F 3，4，5，6，-4F 3，4，5，6，-4F
NO W Y X R 2 R 1 R m
553 554 555 556 557 558 559 560 561 562 563 564 565 566 567 568 569 570 571 572 573 574 575 576 577 578 579 580 581 582 583 584 585 586 587 588 589 590 591 592 593 594 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 O O O O S S S S S S S S S S S S S S S S S S S S S S O O O O O O O O O O O O O O O O Cl Cl Cl Cl F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F F CH 3 CH 3 CH 3 CH 3 H H H H H H H H H H H CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 H H H H H H H H H H H CH 3 CH 3 CH 3 CH 3 CH 3 CH 2C≡CH CH 2C≡C-I CH 2C≡C-Cl CH 2C≡C-Br CH 3 CHF 2 CH 2CN CH 2CH 3 CH 2CH 2CH 3 CH 2OCH 2CH 3 CH 2CH＝CH 2 CH 2C≡CH CH 2C≡C-I CH 2C≡C-Cl CH 2C≡C-Br CH 3 CHF 2 CH 2CN CH 2CH 3 CH 2CH 2CH 3 CH 2OCH 2CH 3 CH 2CH＝CH 2 CH 2C≡CH CH 2C≡C-I CH 2C≡C-Cl CH 2C≡C-Br CH 3 CHF 2 CH 2CN CH 2CH 3 CH 2CH 2CH 3 CH 2OCH 2CH 3 CH 2CH＝CH 2 CH 2C≡CH CH 2C≡C-I CH 2C≡C-Cl CH 2C≡C-Br CH 3 CHF 2 CH 2CN CH 2CH 3 CH 2CH 2CH 3 3，4，5，6，-4F 3，4，5，6，-4F 3，4，5，6，-4F 3，4，5，6，-4F - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
NO W Y X R 2 R 1 R m
595 596 597 598 599 600 601 602 603 604 605 606 607 608 609 610 611 612 613 614 615 616 617 618 619 620 621 622 623 624 625 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1 1 O O O O O O S S S S S S S S S S S S S S S S S S S S S S O O O F F F F F F F F F F F F F F F F F F F F F F F F F F F F CH 3 CF 3 CN CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 H H H H H H H H H H H CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 H H H CH 2OCH 2CH 3 CH 2CH＝CH 2 CH 2C≡CH CH 2C≡C-I CH 2C≡C-Cl CH 2C≡C-Br CH 3 CHF 2 CH 2CN CH 2CH 3 CH 2CH 2CH 3 CH 2OCH 2CH 3 CH 2CH＝CH 2 CH 2C≡CH CH 2C≡C-I CH 2C≡C-Cl CH 2C≡C-Br CH 3 CHF 2 CH 2CN CH 2CH 3 CH 2CH 2CH 3 CH 2OCH 2CH 3 CH 2CH＝CH 2 CH 2C≡CH CH 2C≡C-I CH 2C≡C-Cl CH 2C≡C-Br CH 2C≡CH CH 2C≡CH CH 2C≡CH - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
Table 2:
NO W Y X R 2 R 1 R m
626 627 628 629 630 631 632 633 634 635 636 637 638 639 640 641 642 643 644 645 646 647 648 649 650 651 652 653 654 655 656 657 658 659 660 661 662 663 664 665 666 667 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0 0 0 0 0 0 O O O O O O O O O O O O O O O O O O O O O O O O S S S S S S S S S S S S O O O O O O F F F F F F Cl Cl Cl Cl Cl Cl F F F F F F Cl Cl Cl Cl Cl Cl F F F F F F Cl Cl Cl Cl Cl Cl F F F F F F H H H CH 3 CH 3 CH 3 H H H CH 3 CH 3 CH 3 H H H CH 3 CH 3 CH 3 H H H CH 3 CH 3 CH 3 H H H CH 3 CH 3 CH 3 H H H CH 3 CH 3 CH 3 H H H CH 3 CH 3 CH 3 CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I - 3-F 4-F - 3-F 4-F - 3-F 4-F - 3-F 4-F - 3-F 4-F - 3-F 4-F - 3-F 4-F - 3-F 4-F - 3-F 4-F - 3-F 4-F - 3-F 4-F - 3-F 4-F - 3-F 4-F - 3-F 4-F
NO W Y X R 2 R 1 R m
668 669 670 671 672 673 674 675 676 677 678 679 680 681 682 683 684 685 686 687 688 689 690 691 692 693 694 695 696 697 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 O O O O O O O O O O O O O O O O O O S S S S S S S S S S S S Cl Cl Cl Cl Cl Cl F F F F F F Cl Cl Cl Cl Cl Cl F F F F F F Cl Cl Cl Cl Cl Cl H H H CH 3 CH 3 CH 3 H H H CH 3 CH 3 CH 3 H H H CH 3 CH 3 CH 3 H H H CH 3 CH 3 CH 3 H H H CH 3 CH 3 CH 3 CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I CH 2C≡C-I - 3-F 4-F - 3-F 4-F - 3-F 4-F - 3-F 4-F - 3-F 4-F - 3-F 4-F - 3-F 4-F - 3-F 4-F - 3-F 4-F - 3-F 4-F
Measure through biological screening, the benzoxazine lopps compound of the heterocyclic substituted of general formula of the present invention (I) has extraordinary biological activity, the part of compounds weeding activity is better than the conventional weedicide of use at present, when the low dosage of 18.75ga.i/ha is used, to preventive effect 〉=90% of most of broadleaf weeds.And cauline leaf is handled Chinese sorghum, corn, paddy rice, Soybean and Other Crops safety behind the bud.
Embodiment:
Embodiment 1: the 120th compound N-(7-fluoro-3-oxygen 4-proyl-1,4-benzoxazinone-6-yl) phthalic imidine (NO.120) in the preparation table.
Reaction formula is:
Get the amino benzoxazinone 1.82g of 7-fluoro-6-, be dissolved in the 20ml glacial acetic acid, add the 1.77g Tetra hydro Phthalic anhydride, reflux is 4 hours then.Cooling is poured in the 200ml frozen water, filters out solid, washing, and drying, precipitation gets intermediate.
Add 0.36gNaH in the there-necked flask, be dissolved among the 150mlDMF, be cooled to 0-5 ℃ under stirring, slowly drip above-mentioned intermediate/50mlDMF, drip to finish, stirring at room half an hour, slowly drip the 1.2g propargyl bromide then under the room temperature, dropwise, room temperature reaction 6 hours, in the impouring frozen water, use ethyl acetate extraction, washing, drying, the post branch obtains compound (NO.120) 2.66g, yield 76%.
NMR：4.25(S，2H)4.69(d，2H)6.28(S，1H)7.30-7.68(m，6H)
Embodiment 2: the 626th compound N-(7-fluoro-3-oxygen 4-iodine proyl-1,4-benzoxazinone-6-yl) hexamethylene-1-alkene-1 in the preparation table, 2-dicarboximide (NO.626).
Its reaction formula is:
Get the amino benzoxazinone 1.82g of 7-fluoro-6-, be dissolved in the 20ml glacial acetic acid, add 1.83g 3,4,5, the 6-Tetra Hydro Phthalic Anhydride, reflux is 4 hours then.Cooling is poured in the 200ml frozen water, filters out solid, washing, and drying, precipitation gets intermediate.
Add 0.36gNaH in the there-necked flask, be dissolved among the 150mlDMF, be cooled to 0-5 ℃ under stirring, slowly drip above-mentioned intermediate/50mlDMF, drip to finish, stirring at room half an hour, slowly drip the 1.2g propargyl bromide then under the room temperature, dropwise, room temperature reaction 6 hours is in the impouring frozen water, use ethyl acetate extraction, washing, drying, precipitation obtains intermediate two.
Above-mentioned intermediate two is dissolved in the 200ml acetone, adds 4.5gN-iodo succimide and 0.2g Silver Nitrate, stirring at room reaction 24 hours, and the post branch obtains compound (NO.626) 2.49g, yield 52%.
NMR：3.6-3.8(m，8H)4.25(S，2H)4.72(d，2H)7.30(d，2H)
Application Example 1: potted plant weeding test
(1) reagent
Accurately take by weighing sample, after the The suitable solvent dissolving, add small amounts of emulsifiers, adding distil water is settled to 10ml and adopts suitable spraying machine sprinkling again, and reduced unit's area dose is 18.75ga.i/ha.
(2) examination material
Dicotyledonously select lamb's-quarters (Chenopodium album), fennel fiber crops (Abutilon theophrast) i, recessed amaranth (Amaranthus ascedense) for use, unifacial leaf is selected lady's-grass (Digitaria sanguinalis), barnyard grass grass (Echinochloacrus-galli), Herba Setariae Viridis (Setaria viridis) for use.
(3) cultivation of examination material plant
At sectional area 64cm 2The plastic tub alms bowl in quantitatively load onto, flatten, water permeable, choose full seed, lady's-grass of the same size, barnyard grass grass, Herba Setariae Viridis, fennel fiber crops, lamb's-quarters, recessed amaranth seed, divide single, double cotyledon plant to divide the pot culture kind, respectively account for 1/3 of alms bowl area, cover thick thin the going up and trickle of 1cm, place hot-house culture.Treat that unifacial leaf examination material grows to 1 heart stage of 1 leaf, dicotyledonous examination material grows to 2 leaf periods, carry out seedling with soup after the cauline leaf spraying handle, soil treatment before the seedling is carried out in the sowing of examination material next day.Put back to the greenhouse subsequently.
(4) test
15 back range estimation overground part growing states calculate growth inhibition ratio, growth inhibition ratio (%)=100 (contrast plant height-processing plant height)/contrast plant height.Carry out the weeding activity classification according to growth inhibition ratio: A level growth inhibition ratio＞90%; B level growth inhibition ratio 75～90%; C level growth inhibition ratio 50～75%; D level growth inhibition ratio is less than 50%.
Part of compounds of the present invention such as compound N O.69,120,137,626 etc. respectively with the amount of application of 18.75ga.i/ha to potted plant examination material plant bud after cauline leaf handle, suppress the virulence effect and see Table 3.
Table 3: potted plant weeding test
Recessed amaranth of sample lady's-grass barnyard grass grass Herba Setariae Viridis lamb's-quarters fennel fiber crops
NO.69 D D D B B A
120 D D D A A A
137 D D D A A A
626 D D D A A A
As table 3 as can be known: four compounds of test all have good preventive effect to broadleaf weeds under the low dosage of 18.75ga.i/ha, but invalid to gramineous weeds.
Application Example 2: crop safety test.
Choose full, the of the same size paddy rice Oryza of seed material sativa, wheat Triticum aestivum, corn Zeamays, Chinese sorghum sorghum vulgare, soybean Glvcine max and rape Brassica campestris seed, use 0.1%HgCl 2Sterilization 5min, the back leaches and puts into little porcelain dish (putting wetting thieving paper) at 25 ℃ of growth chamber vernalization 24h with steaming filling water logging kind 12h, gets size and 10 in the long consistent seed of bud, is sowed at 64cm 2Quantitatively in the plastic tub alms bowl of dress soil, cover thick fine earth of 1cm and trickle, place hot-house culture.Treat that unifacial leaf examination material grows to 1 heart stage of 1 leaf, dicotyledonous examination material grows to 2 leaf periods, with 150,75,37.5,18.75,9.375, the 4.6875ga.i./ha soup carry out seedling after the cauline leaf spraying handle, the examination material is sowed and is carried out the preceding soil treatment of seedling next day, be contrast with spraying solvent and clear water respectively, twice repetition, handle the examination material and place hot-house culture, observe the crop symptom of being injured behind the 15d, range estimation overground part growth inhibition ratio.Growth inhibition ratio (%)=100 (contrast plant height-processing plant height)/contrast plant height, according to growth inhibition ratio estimation crop IC ' 10 values, and in conjunction with weeds IC 90Value is pressed IC ' 10/IC 90Calculate selectivity index (Z), safety grades standard: A: Z＞4B 2＜Z＜4 C Z＜2 can be considered safety more than the B level.
Compound of the present invention (NO.120) the results are shown in Table 4 to the safety experiment of crop
Table 4: safety experiment
Dosage ga.i/ha rice and wheat rape corn and Chinese sorghum soybean
Sample
150 C C C C C C
75 C C C C B C
NO.120 37.5 B C C B A B
18.75 A B C A A A
9.375 A B C A A A
4.6875 A A B A A A
As table 4 as seen: compound N O.120 under the dosage of 37.5ga.i/ha to high safety beam; 18.75ga.i/ha than under the low dosage to paddy rice, corn and soybean safety.But it is dangerous to rape and wheat.

Claims (4)

1 one kinds of heterocyclic substituted benzo oxazine lopps compounds is characterized in that having following general structure (I):
Figure C031182260002C1
Its Chinese style (I) Het is:
Figure C031182260002C2
Y＝O，S；
W＝0，1；
X is F, Cl, CH 3, CF 3, CN;
R 2Be H, CH 3, Ph;
R is F, Cl, Br, CH 3, NO 2
M represents substituent number optional 0,1,2,3,4;
When Het=(II), R 1Be CH 3, CHF 2, CH 2CH 3, CH 2CN, CH 2CH 2CH 3,
CH 2CH＝CH 2，CH 2C≡CH，CH 2C≡C-Br，CH 2C≡C-Cl，CH 2C≡C-I，
CH 2OCH 2CH 3；
When Het=(III), R 1Only be CH 2C ≡ C-I;
The benzoxazine lopps compound of 2 a kind of heterocyclic substituted according to claim 1 is characterized in that the X in the general formula (I) is a fluorine; Y is O; W is 1; R 1Be proyl, iodine proyl; R 2Be H; M=0 or R are fluorine;
The preparation method of the benzoxazine lopps compound of 3 heterocyclic substituted according to claim 1 and 2 is characterized in that available following synthetic route obtains;
Figure C031182260003C1
W in the formula, X, Y, R, R 1, R 2, m defines with claim 1;
4 purposes according to claim 1 and 2 described heterocyclic substituted benzo oxazine lopps compounds is characterized in that having weeding activity, under low dosage, broadleaf weeds are had excellent herbicidal, and to Chinese sorghum, corn, paddy rice, soybean crops safety.
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