CN104774179A - Halogenated alkenyl pyrazole compound and preparation method thereof - Google Patents
Halogenated alkenyl pyrazole compound and preparation method thereof Download PDFInfo
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- CN104774179A CN104774179A CN201410011904.4A CN201410011904A CN104774179A CN 104774179 A CN104774179 A CN 104774179A CN 201410011904 A CN201410011904 A CN 201410011904A CN 104774179 A CN104774179 A CN 104774179A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/16—Halogen atoms or nitro radicals
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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Abstract
The present invention relates to a halogenated alkenyl pyrazole compound and a preparation method thereof. The prior art has disadvantages of complex preparation process, high production cost, and toxic-side effects on organisms. The compound of the present invention is represented by a general formula I or general formula II. The preparation steps comprise: taking a 1-vinyl-3,5-dimethyl pyrazole compound, dissolving in carbon tetrachloride, carrying out stirring mixing, and heating to a temperature of 60 DEG C, wherein a molar ratio of the raw material to the solvent is 1:10-20; adding N-chlorosuccinimide and N-bromosuccinimide, and carrying out constant temperature for 4-7 h at a temperature of 60 DEG C; removing the solvent; dissolving with ethyl acetate, and adding a silica gel; drying; and loading onto a 200-300 mesh silica gel column to separate to prepare the halogenated alkenyl pyrazole compound. According to the present invention, advantages of simple preparation, no environmental pollution during the preparation process, and good sterilization activity are provided.
Description
Technical field
the invention belongs to pyrazole compound, specifically a kind of haloalkenyl group pyrazole compound and preparation method thereof.
Background technology
pyrazole compound has strong physiology and the heterogeneous ring compound of pharmacologically active, and because its toxicity is low, has and select systemic activity, the advantage such as safe and efficient, pyrazole compound has become the important source material of novel agrochemical exploitation.
the shortcoming of prior art pyrazole compound is:
1. complicated process of preparation, production cost is high.Such as: pyraclostrobin is the sterilant of BASF AG's latest model methoxy acrylic, international patent: WO2011113884A1, and structural formula is as follows:
this compound fungicidal activity is high, is widely used as the environmentally friendly sterilant of one.Due to its complex synthetic route, preparation trouble, limits it and further expands popularization and use.
to biological toxic side effect.Such as: ethiprole (fipronil), international patent: WO2012007938A1, be one and have representational aromatic base pyrazoles sterilant, structural formula is as follows:
the shortcoming of this compound is: to aquatic toxicity such as honeybees very greatly, simultaneously unfriendly to environment, constrain its widely using on agricultural chemicals.
therefore invent that a kind of preparation technology is simple, fungicidal activity is high, environmentally friendly, the serial pyrazole compound that has no side effect and preparation method thereof is very necessary.
the present invention, by a large amount of experiments, uses pyrazole compound as raw material, is dissolved in tetracol phenixin, and mixing, intensification, add N-chlorosuccinimide or N-bromo-succinimide, isothermal reaction 4-7 hour, obtained serial haloalkenyl group pyrazole compound.The compounds of this invention preparation technology is simple, fungicidal activity is high, environmentally friendly.
through extensively consulting patent documentation and domestic and international public publication, be showed no the haloalkenyl group pyrazole compound identical with structure of the present invention.
Summary of the invention
the object of this invention is to provide simple, active high, the environment amenable serial haloalkenyl group pyrazole compound of a kind of preparation technology;
another object of the present invention is to provide the preparation method of this haloalkenyl group pyrazole compound.
content of the present invention is as follows:
one class haloalkenyl group pyrazole compound, is represented by formula I or general formula II:
formula I formula II
r in formula I
1
for the one in fluorine, chlorine or bromine atom; R
2
for hydrogen atom, methyl, phenyl, to the one in fluorophenyl, rubigan; R
3
for to fluorine atom, to chlorine, to bromine, to methyl, to methoxyl group, 2,4 dichloro benzene base, 2,4,5-trichlorophenyl, 2,4,6-trichlorophenyl, the one in 2,5-dichlorophenyl, 2-methyl-5-chloro, 2,3,4-trichlorines, 2-methyl-4,5-dichlorophenyl;
r in formula II
4
for the one in fluorine, chlorine and bromine; R
5
for hydrogen, methyl, phenyl, to the one in fluorophenyl, rubigan; R
6
for to fluorine, to chlorine, to bromine, to methyl, to methoxyl group, 2,4 dichloro benzene base, 2,4,5-trichlorophenyl, 2,4,6-trichlorophenyl, the one in 2,5-dichlorophenyl, 2-methyl-5-chloro, 2,3,4-trichlorines, 2-methyl-4,5-dichlorophenyl.
one class haloalkenyl group pyrazole compound, preparation process is as follows:
(1) get 1-vinyl-3,5-dimethylpyrazole compounds to be dissolved in tetracol phenixin, to be uniformly mixed, be warming up to 60 DEG C, the mol ratio of 1-vinyl-3,5-dimethylpyrazole compounds and tetracol phenixin is 1: 10-20;
(2) in step (1) product, N-chlorosuccinimide, N-bromo-succinimide is added, 60 DEG C of isothermal reaction 4-7 hour, the mol ratio 1: 1-2 of 1-vinyl-3,5-dimethylpyrazole compounds and N-chlorosuccinimide or N-bromo-succinimide;
(3) step (2) product is removed desolventizing;
(4) to step (3) product acetic acid ethyl dissolution, silica gel is added;
(5) step (4) product is dry, except desolventizing;
(6) step (5) product is crossed 200-300 order silicagel column to be separated, obtained haloalkenyl group pyrazole compound.
main points of the present invention are:
use the present inventor's patent No.: the 1-vinyl-3 of 201310551791.2 preparations, 5-dimethyl pyrazole compounds is as raw material, be dissolved in tetracol phenixin, mixing, intensification, add N-chlorosuccinimide or N-bromo-succinimide, isothermal reaction 4-7 hour, obtained serial haloalkenyl group pyrazole compound.
the solvent that the present invention uses is tetracol phenixin, molecular formula CCl
4
, molecular weight 153.84, liquid, colourless, volatile, nonflammable.Pyrazole compound can dissolve in tetracol phenixin completely as raw material.
the present invention has synthesized serial haloalkenyl group pyrazole compound, and this series compound title, structural formula, fusing point are in table one; Spectroscopic data is in table two.
table one: haloalkenyl group pyrazole compound title, structural formula and fusing point
table two: the nuclear-magnetism of haloalkenyl group pyrazole compound, infrared, mass-spectrometric data
advantage of the present invention is:
1. invented a series of haloalkenyl group pyrazole compound having no report;
2. this serial haloalkenyl group pyrazole compound preparation process is simple, preparation process non-environmental-pollution;
3. this series compound has good fungicidal activity.
Embodiment
below by embodiment, the present invention will be further described.
embodiment 1:
compound 4-chloro-1-(1-(4-the fluorophenyl of sequence number 3 in preparation table one) 2-phenyl vinyl)-3,5-dimethyl-1 hydrogen-pyrazoles; Get 5.8g 1-(1-(4-fluorophenyl)-2-phenyl vinyl)-3,5-dimethyl-1 hydrogen-pyrazoles is dissolved in tetracol phenixin, be warming up to 60 DEG C, add 2.6g N-chlorosuccinimide to stir, be incubated 6 hours, be spin-dried for reaction solution, reaction solution adds ethyl acetate, add 200-300 order silica gel to be spin-dried for silicagel column and to obtain the chloro-1-(1-(4-fluorophenyl of pure target product 4-) 2-phenyl vinyl)-3,5-dimethyl-1 hydrogen-pyrazoles.The present embodiment reaction formula is as follows:
recording the present embodiment product nuclear magnetic data through experiment is:
1
h NMR (400MHz, CDCl3) δ 7.23-7.15(m, 7H), 7.00-6.96 (m, 2H), 6.80 (s, 1H), 2.29 (s, 3H), 2.00 (s, 3H).
experiment records the present embodiment product infrared data and is: IR:max(thin film) (cm
-1
)
=3114,2995,2942,1654,1566,1435,1263 ,1078,833,675.
experiment records the present embodiment product mass spectra data and is: ESI-MS: m/z (%): 327 [M+H]
+
.
embodiment 2:
the bromo-1-(2 of the bromo-1-(2-of compound 4-of sequence number 12 in preparation table one, 4,5-trichlorophenyl) vinyl)-3,5-dimethyl-1 hydrogen-pyrazoles; Get 6.1g 3,5-dimethyl-1-(1-(2,4,5-trichlorophenyl) vinyl)-1 hydrogen-pyrazoles is dissolved in tetracol phenixin, is warming up to 70 DEG C, add 7.2g, N-bromo-succinimide stirs, 60 DEG C of insulation reaction 5 hours, question response terminates, and is spin-dried for reaction solution, and reaction solution adds ethyl acetate, add 200-300 order silica gel to be spin-dried for silicagel column and to obtain the pure chloro-1-(1-(2 of target product 4-, the chloro-2-aminomethyl phenyl of 4,5-tri-) vinyl)-3,5-dimethyl-1 hydrogen-pyrazoles.The present embodiment reaction formula is as follows:
recording the present embodiment product nuclear magnetic data through experiment is:
1
h NMR (400MHz, CDCl3) δ 7.56 (s, 1H), 7.55(s, 1H), 6.85 (s, 1H), 2.21 (s, 3H), 2.13 (s, 3H).
experiment records the present embodiment product infrared data and is: IR:max(thin film) (cm
-1
)
=3111,2987,2894,1662,1557,1463,1392,1076,923,834,797781.
experiment records the present embodiment product mass spectra data and is: ESI-MS: m/z (%): 461 [M+H]
+
.
embodiment 3:
in preparation table one, sequence number is the compound 4-bromo-1-(1-(4-chloro-2-methyl phenyl of 18)-2-phenyl vinyl)-3,5-dimethyl-1 hydrogen-pyrazoles; Get 6.5g 1-(1-(4-chloro-2-methyl phenyl)-2-phenyl vinyl)-3,5-dimethyl-1 hydrogen-pyrazoles is dissolved in tetracol phenixin, be warming up to 65 DEG C, add 3.5g N-bromo-succinimide to stir, 60 DEG C of insulation reaction 4 hours, question response terminates, be spin-dried for reaction solution, reaction solution adds ethyl acetate, add 200-300 order silica gel to be spin-dried for silicagel column and to obtain pure target product 4-bromo-1-(1-(4-chloro-2-methyl phenyl)-2-phenyl vinyl)-3,5-dimethyl-1 hydrogen-pyrazoles.The present embodiment reaction formula is as follows:
recording the present embodiment product nuclear magnetic data through experiment is:
1
h NMR (400MHz, CDCl
3
) δ 7.21-7.16 (m, br, 5H), 7.11-7.04 (m, br, 4H), 2.31 (s, 3H), 2.21 (s, 3H), 1.95 (s, 3H);
experiment records the present embodiment product infrared data and is: IR:max(thin film) (cm
-1
)
=3126,2983,2897,1577,1472,1386,1165,947, 885,694,519;
experiment records the present embodiment product mass spectra data and is: ESI-MS: m/z (%): 402 [M+H]
+
.
embodiment 4:
the bromo-1-(2-(2-chloro-phenyl-of the compound 4-of sequence number 46 in preparation table one)-1-(2,4-dichlorophenyl) vinyl)-3,5-dimethyl-1 hydrogen-pyrazoles; Get 6.5g 1-(2-(2-chloro-phenyl-)-1-(2,4-3,5-dimethylphenyl) vinyl)-3,5-dimethyl-1 hydrogen-pyrazoles is dissolved in 20ml tetracol phenixin, be warmed up to 80 DEG C, add 3.6g N-bromo-succinimide, 80 DEG C of insulation reaction 6 hours, question response terminates, and uses Rotary Evaporators to be spin-dried for reaction solution; Add ethyl acetate; Add silica gel, be spin-dried for, cross silicagel column and obtain the bromo-1-(2-(2-chloro-phenyl-of pure target product 44-)-1-(2,4-dichlorophenyl) vinyl)-3,5-dimethyl-1 hydrogen-pyrazoles.The present embodiment reaction formula is as follows:
recording the present embodiment product nuclear magnetic data through experiment is:
1
h NMR (400MHz, CDCl
3
) δ 7.27 (m, 3H), 7.14 (m, 5H), 5.98 (s, 1H), 2.23 (s, 3H), 2.05 (s, 3H), 1.89 (s, 3H), 1.78 (s, 3H);
experiment records the present embodiment product infrared data and is: IR:max(thin film) (cm
-1
)
=3125,2995,2894,1658,1557,1463,1319,1062,937,824,749,727,592;
experiment records the present embodiment product mass spectra data and is: ESI-MS: m/z (%): 417 [M+H]
+
.
embodiment 5:
measure through Sheng Ceanping center, Zhejiang Provincial Chemical Engineering Research Inst, part of compounds biological activity determination result of the present invention is as follows:
table three: haloalkenyl group pyrazole compound indoor bactericidal activity tests result
above-described embodiment is only section Example of the present invention, is not used for representing the present invention.Each compound prepared by the present invention all has sterilization effect.All within principle of the present invention, any modifications and variations done, all within protection scope of the present invention.
Claims (3)
1. a class haloalkenyl group pyrazole compound, is represented by formula I or general formula II:
Formula I formula II
R in formula I
1for the one in fluorine, chlorine or bromine atom; R
2for hydrogen atom, methyl, phenyl, to the one in fluorophenyl, rubigan; R
3for to fluorine atom, to chlorine, to bromine, to methyl, to methoxyl group, 2,4 dichloro benzene base, 2,4,5-trichlorophenyl, 2,4,6-trichlorophenyl, the one in 2,5-dichlorophenyl, 2-methyl-5-chloro, 2,3,4-trichlorines, 2-methyl-4,5-dichlorophenyl;
R in formula II
4for the one in fluorine, chlorine and bromine; R
5for hydrogen, methyl, phenyl, to the one in fluorophenyl, rubigan; R
6for to fluorine, to chlorine, to bromine, to methyl, to methoxyl group, 2,4 dichloro benzene base, 2,4,5-trichlorophenyl, 2,4,6-trichlorophenyl, the one in 2,5-dichlorophenyl, 2-methyl-5-chloro, 2,3,4-trichlorines, 2-methyl-4,5-dichlorophenyl.
2. the class haloalkenyl group pyrazole compound according to claims 1, preparation process is as follows:
(1) get 1-vinyl-3,5-dimethylpyrazole compounds to be dissolved in tetracol phenixin, to be uniformly mixed, be warming up to 60 DEG C, the mol ratio of 1-vinyl-3,5-dimethylpyrazole compounds and tetracol phenixin is 1: 10-20;
N-chlorosuccinimide, N-bromo-succinimide is added in step (1) product, 60-80 DEG C of isothermal reaction 4-7 hour, the mol ratio 1: 1-2 of 1-vinyl-3,5-dimethylpyrazole compounds and N-chlorosuccinimide or N-bromo-succinimide;
(3) step (2) product is removed desolventizing;
(4) to step (3) product acetic acid ethyl dissolution, silica gel is added;
(5) step (4) product is dry, except desolventizing;
(6) step (5) product is crossed 200-300 order silicagel column to be separated, obtained haloalkenyl group pyrazole compound.
3. compound described in claim 1 has the biological activity of agricultural chemicals aspect.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114874144A (en) * | 2022-03-28 | 2022-08-09 | 曲靖师范学院 | Process for preparing 4-bromo-N-arylpyrazole compound |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6216404A (en) * | 1985-07-12 | 1987-01-24 | Mitsui Toatsu Chem Inc | Industrial antifungal composition |
DE3719326A1 (en) * | 1987-06-10 | 1989-01-05 | Bayer Ag | Fungicidal active substance combination |
US4894381A (en) * | 1987-06-27 | 1990-01-16 | Bayer Aktiengesellschaft | Microbicidal (azolyl-vinyl)-phenol alkenyl ethers |
-
2014
- 2014-01-12 CN CN201410011904.4A patent/CN104774179B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6216404A (en) * | 1985-07-12 | 1987-01-24 | Mitsui Toatsu Chem Inc | Industrial antifungal composition |
DE3719326A1 (en) * | 1987-06-10 | 1989-01-05 | Bayer Ag | Fungicidal active substance combination |
US4894381A (en) * | 1987-06-27 | 1990-01-16 | Bayer Aktiengesellschaft | Microbicidal (azolyl-vinyl)-phenol alkenyl ethers |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114874144A (en) * | 2022-03-28 | 2022-08-09 | 曲靖师范学院 | Process for preparing 4-bromo-N-arylpyrazole compound |
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