CN100435636C - Dichloropropylene type pesticide - Google Patents

Dichloropropylene type pesticide Download PDF

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CN100435636C
CN100435636C CNB2006100465682A CN200610046568A CN100435636C CN 100435636 C CN100435636 C CN 100435636C CN B2006100465682 A CNB2006100465682 A CN B2006100465682A CN 200610046568 A CN200610046568 A CN 200610046568A CN 100435636 C CN100435636 C CN 100435636C
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王正权
李彦龙
周丽平
王俊春
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Jiangsu Sword Agrochemicals Co Ltd
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Abstract

The present invention relates to a dichloro-propylene type pesticide. The compounds of the present invention have a general formula (A) of active components. On the basis of original researched dichloro-propylene type pesticides, the present invention reserves the active components of compounds, changes other variable genes, and emphatically researches and develops a pesticide which is composed of compounds (1) to (4) and has the advantages of novel structure, high efficiency, low toxicity and good disinsection effect. Compared with the lead compound S-1812, the present invention has identical or better disinsection effect, the disinsection spectrums of partial compounds are wide, and the disinsection activity is high.

Description

Dichloropropylene type pesticide
Technical field:
The present invention relates to a kind of insecticide, particularly a kind of dichloropropene insecticide.
Background technology:
Because human attention to environmental issue is had higher requirement to the toxicity of agricultural chemicals and to the influence of environment, high malicious organophosphorous pesticide is because toxicity and environmental problem and will be eliminated gradually.And active high, the low toxic pesticide that Environmental compatibility is good is the target of developing in recent years.In recent years, researched and developed many insecticides new and effective, low toxicity and substituted high malicious organophosphorous pesticide, dichloropropene (Pyridalyl class) insecticide is a class wherein.
SUMITOMO CHEMICAL company proposed (US 5922880 for JPn, kokai Tokkyo koho JP09194418) Pyridalyl class new pesticides in 1997, and trade name is S-1812, and chemical structural formula is as follows:
This compound is mainly used in cotton, fruit, vegetables etc., and lepidoptera pest is had high susceptibility, also can be mixed with various medicaments, plays synergistic effect.In addition, SUMITOMO CHEMICAL department has also reported many similar compounds in succession, and activity is mostly arranged.
Summary of the invention:
Purpose of the present invention is exactly on the basis of above-mentioned research, keeps the active part of compound, changes other variable gene, develops the insecticide with efficient insecticide effect of a class new construction.
In order to address the above problem, the technical solution used in the present invention is that a kind of dichloropropylene type pesticide, this insecticide have following general structure (A):
Figure C20061004656800041
Ar is a 4-trifluoro ethoxy phenyl amino carbonyl, 2 in the formula, 7-dimethyl benzofuran carbonyl, 2,2-dimethyl benzofuran amino carbonyl, 2-chloropyridine carbonyl, 5-chloropyridine base, 2,2,3,3-tetramethyl cyclopropyl carbonyl, anthraquinonyl, 2-methyl benzofuran amino, 7,7-diformazan-benzofuranyl.
The noval chemical compound that has specifically synthesized following structure:
Compound (I): 3,5-two chloro-4-(3-(N-(4-trifluoro ethoxy phenyl) carbamoyloxy) propoxyl group)-1-(3,3-two chloro-2-allyloxys) benzene
Figure C20061004656800042
Compound (II): 3-[3-[2,6-two chloro-4-[(3,3-two chloro-2-pi-allyls) the oxygen base] phenoxy group] propoxyl group] carbonyl-2, the 7-dimethyl benzofuran
Figure C20061004656800043
Compound (III): 5-[3-[2,6-two chloro-4-[(3,3-two chloro-2-pi-allyls) the oxygen base] phenoxy group] acylamino-]-2, the 2-dimethyl benzofuran
Figure C20061004656800051
Compound (IV): 3-[3-[2,6-two chloro-4-[(3,3-two chloro-2-pi-allyls) the oxygen base] phenoxy group] the third oxygen carbonyl]-the 2-chloropyridine
Figure C20061004656800052
Compound (V): 2-[3-[2,6-two chloro-4-[(3,3-two chloro-2-pi-allyls) the oxygen base] phenoxy group] propoxyl group]-the 5-chloropyridine
Figure C20061004656800053
Compound (VI): 3,5-two chloro-[4-[3-(2,2,3, the 3-tetramethyl) cyclopropyl] carbonyl propoxyl group]-1-(3,3-two chloro-2-pi-allyls) oxygen base) benzene
Figure C20061004656800054
Compound (VII): 2-[3-[2,6-two chloro-4-[(3,3-two chloro-2-pi-allyls) the oxygen base] phenoxy group] propoxyl group] anthraquinone
Figure C20061004656800055
Compound (VIII) 5-[3-[2,6-two chloro-4-[(3,3-two chloro-2-pi-allyls) the oxygen base] phenoxy group] propoxyl group]-2-methyl benzofuran
Figure C20061004656800061
Compound (IX): 2-[3-[2,6-two chloro-4-[(3,3-two chloro-2-pi-allyls) the oxygen base] phenoxy group] propoxyl group]-7, the 7-dimethyl benzofuran
Figure C20061004656800062
The synthetic method of the compound of above-mentioned new construction is as follows:
(1) 1,1,3-tri chloropropene synthetic
CCl 3CH 2CH 2Cl→CCl 2＝CHCH 2Cl+HCl
This reaction is by 1,1,1, and 3-tetrachloro propane is with anhydrous FeCl 2Be catalyst, make 1,1, the 3-tri chloropropene through heating desalination acid.
(2) 2,6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenoxypropanol synthetic:
Figure C20061004656800063
This reaction is by hydroquinones and 1,1, the reaction of 3-tri chloropropene, make acid binding agent with Anhydrous potassium carbonate and carry out condensation with methyl alcohol as solvent, and then make solvent with toluene, catalyzer made by triethylamine and thionyl chloride carries out chlorination reaction, make 2,6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenol, at last again with the condensation of 3-bromopropyl alcohol.Obtain end product.
(3) compound (I) is synthetic:
This reaction is reacted the generation isocyanates by trifluoro ethoxy aniline and solid phosgene in ethyl acetate solvent, then under the triethylamine catalyzer with 2,6-two chloro-4-(3 ', 3 '-dichloro) the allyloxy phenoxypropanol reacts in benzene and obtains compound (I).
(4) compound (II) is synthetic
Figure C20061004656800081
This reaction 2,6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenol and 1, the 3-dibromopropane is at N, and in the dinethylformamide solvent, potash is made the acid binding agent room temperature reaction, can make intermediate 2,6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenoxy group N-Propyl Bromides, and then adding benzofurancarboxylic acid room temperature reaction obtains compound (II).
(5) compound (III) is synthetic:
Figure C20061004656800082
Reaction by benzofuran amine and solid phosgene in ethyl acetate solvent, reaction generates the benzofuran isocyanates, then under triethylamine catalysis with 2,6-two chloro-4-(3 ', 3 '-dichloro) the allyloxy phenoxypropanol reacts in benzene and obtains compound (III).
(6) compound (IV) is synthetic:
Figure C20061004656800091
This reaction 2,6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenol and 1, the 3-dibromopropane is at N, in the dinethylformamide solvent, potash is made the acid binding agent room temperature reaction, can make intermediate 2,6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenoxy group N-Propyl Bromide is then at N, in the dinethylformamide solvent, potash is made acid binding agent and 2-chlorine apellagrin room temperature reaction, obtains compound (IV).
(7) compound (V) is synthetic:
Figure C20061004656800092
This is reflected in the n-hexane solvent, and 2,6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenoxypropanol and 2, the 5-dichloropyridine obtains compound (V) through back flow reaction in the presence of liquid caustic soda.
(8) compound (VI) is synthetic:
Figure C20061004656800101
This reaction 2,6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenol and 1, the 3-dibromopropane is at N, in the dinethylformamide solvent, potash is made the acid binding agent room temperature reaction, can make intermediate 2,6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenoxy group N-Propyl Bromide, then with chrysanthemumic acid at N, in the dinethylformamide solvent, potash is made acid binding agent, obtains compound (VI) through room temperature reaction.
(9) compound (VII) is synthetic:
Figure C20061004656800102
This is reflected in the n-hexane solvent, 2,6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenoxypropanol and 2-chloroquinoline in the presence of sodium hydroxide solution, obtain compound (VII) through back flow reaction.
(10) compound (VIII) is synthetic:
Figure C20061004656800111
This reaction 2,6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenol and 1, the 3-dibromopropane is at N, and in the dinethylformamide solvent, potash is made the acid binding agent room temperature reaction, can make intermediate 2,6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenoxy group N-Propyl Bromides are then at N, in the dinethylformamide solvent, potash is made acid binding agent and p-aminophenyl and furans, through low-temp reaction, obtains compound (VIII)
(11) compound (IX) is synthetic:
Figure C20061004656800112
Figure C20061004656800121
Reaction divided for five steps carried out, it at first is raw material with the catechol, in methanol solvate, make acid binding agent with Anhydrous potassium carbonate, carry out etherification reaction for 40 ℃ with methylallyl chloride, again through the high temperature transposition, then in xylene solvent, under the catalysis of p-methyl benzenesulfonic acid, carry out ring-closure reaction, obtain benzofuran phenol.
2,6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenol and 1, the 3-dibromopropane is at N, and in the dinethylformamide solvent, potash is made the acid binding agent room temperature reaction, can make intermediate 2,6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenyl-bromide propane.
Last benzofuran phenol and intermediate 2,6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenyl-bromide propane room temperature condensations obtain compound (IX).
According to the method described above, synthesized compound of the present invention.Their analysis data are as shown in table 1;
Table 1:
Compound HNMR(CDCl 3，400M)
I 2.20(m，2H-CH 2-)，4.05(t，2H，-OCH 2-)，4.5((t，2H，-OCH 2-) 4.30(m，2H，-OCH 2CF 3)，4.60(d，2H，-OCH 2-), 6.05 (t, 1H ,=CH-) 6.62 (s, 1H ,-NH-), 6.80～6.95 (m, 4H, phenyl ring), 7.2～7.4 (m, 2H, phenyl ring)
II 1.4～1.45(d，3H，-CH 3)，2.2～2.3(m，2H，-CH 2-)2.42(s，3H，-CH 3) 2.8～3.4(m，2H，-CH 2-)，4.1(t，2H，-OCH 2-), 4.5～4.6 (m, 4H, two-OCH 2-) 4.9 (m, 1H ,-CH-), 6.1 (t, 1H ,=CH), 7.0 (d, 2H, phenyl ring), 7.4 (d, 2H, phenyl ring)
III 1.4(d，3H，-CH 3)，2.1～2.2(m，2H，-CH 2-)，2.7～3.3(m，2H，-CH 2-) 4.0(t，2H，-OCH 2-)，4.4(t，2H，-OCH 2-)，4.6(d，2H，-OCH 2), 4.9 (m, 1H ,-CH-) 6.1 (t, 1H ,=CH), 6.6 (s, 1H ,-NH-), 7.2～7.4 (m, 2H, phenyl ring), 6.8～7.0 (m, 3H, phenyl ring)
IV 2.2～2.3(m，2H，-CH 2-)，4.1～4.2(t，2H，-OCH 2-)，4.5(d，2H，-OCH 2-)， 4.7(t，2H，-OCH 2-) 6.1 (t, H ,=CH-), 6.8 (s, 2H, phenyl ring), 7.3～8.6 (m, 3H, pyridine rings)
V 2.2～2.3(m，2H，-CH 2-)，4.1～4.2(t，2H，-OCH 2-)，4.5(d，2H，-OCH 2-)， 4.6(t，2H，-OCH 2-) 6.1 (m, 1H ,=CH-), 6.7 (d, 1H, pyridine rings), 6.8 (m, 1H, phenyl ring), 7.4～8.1 (m, 2H, pyridine rings)
VI 1.1～1.4 (m, 12H, 4-CH 3)，2.1～2.2(m，2H，-CH 2-)，4.0～4.1(t， 2H，-OCH 2-)，4.3(t，2H，-OCH 2-)4.6(d，2H，-OCH 2-)，6.1(t，1H，＝CH 2), 6.8 (m, 2H, phenyl ring)
VII 2.3～2.4(m，2H，-CH 2-)，4.1～4.2(t，2H，-OCH 2-)，4.5(d，2H，-OCH 2-)， 4.7(t，2H，-OCH 2-) 6.1 (m, 1H ,=CH-), 6.8 (m, 2H, phenyl ring), 6.9～7.9 (m, 6H, benzo pyridines)
VIII 1.3～1.5(d，3H，-CH 3)，2.0～2.2(m，2H，-CH 2-)，2.7～3.3(m，2H，-CH 2-)， 3.4(t，2H，-OCH 2-)4.1(t，2H，-OCH 2-)，4.6(d，2H，-OCH 2-), 4.8 (m, 1H ,-OCH-), 6.1 (t, 1H ,=CH-) 6.4～6.6 (m, 3H, phenyl ring), 6.8 (m, 2H, phenyl ring)
IX 1.5 (s, 6H, 2 ,-CH 3)，2.3(m，2H，-CH 2-)，3.0(s，2H，-CH 2-)，4.1 (t，2H，-OCH 2-)，4.3(t，2H，-OCH 2-)4.5(d，2H，-OCH 2-), 6.1 (m, 1H ,=CH-), 6.7～6.8 (m, 2H, phenyl ring)
Synthetic compound is carried out the insecticidal activity test, the insect of primary dcreening operation test is: mythimna separata, diamond-back moth, broad bean sprout, Tetranychus cinnabarinus, Culex pipiens pallens, brown plant-hopper, test compounds concentration is except that being the 10mg/L to Culex pipiens pallens, all the other insects are 600mg/L, dispenser one day and two days later, calculate insecticidal activity (insecticidal activity=insect death toll ÷ insect sum * 100%) in the dead ratio of insect, test result is shown in Table 2;
Table 2: insecticidal activity primary dcreening operation test result:
Figure C20061004656800141
X is that its structural formula of lead compound (trade name is S-1812) is:
Figure C20061004656800142
Insecticidal activity is at the Compound I I more than 90%, V, VI, VII, and X enters next stage and sieves test again.
To Compound I I, V, VI, VII, the X insecticidal activity is carried out multiple sieve test, and the insect of test is that mythimna separata, not dispenser of diamond-back moth are blank, control drug is efficient chlorine cyanogen, dispenser one day and is two days later calculated insecticidal activity in the dead ratio of insect, test result see Table 3 and table 4 shown in.
Table 3: insecticidal activity is sieved test result (to mythimna separata) again
Figure C20061004656800143
Table 4: insecticidal activity is sieved test result (to diamond-back moth) again
Figure C20061004656800152
The test of pesticide effectiveness proves that compound of the present invention compares with lead compound S-1812, have identical or higher insecticidal effect, and the insecticidal spectrum of part of compounds is wideer, and insecticidal activity is higher.
Embodiment:
Embodiment 1:1,1,3-tri chloropropene synthetic
182 grams 1,1,1 add 0.63 gram frerrous chloride in the 3-tetrachloro propane, be heated to 95 ℃ of reactions 8 hours, air-distillation then.Collect 120～133 ℃ of fractions, 118 grams, be product 1,1, the 3-tri chloropropene.
Embodiment 2:2,6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenol synthetic
In 150ml methyl alcohol, add 18.0 gram hydroquinones, 15.4 grams 1,1, the 3-tri chloropropene, Anhydrous potassium carbonate 18.0 grams, 45 ℃ of reactions 5 hours add the dilution of 150ml water, after the filtration, the mother liquor precipitation, obtain 10.9 gram 4-(3 ', 3 '-dichloro) allyloxy phenol.
Adding 5.7 gram 4-in 50ml toluene (3 ', 3 '-dichloro) allyloxy phenol, 0.035 gram triethylamine, 90 ℃ of following dripping thionyl chloride 7 grams drip off the back and reacted 20 hours under this temperature, add the 18ml saturated sodium bicarbonate solution, through twice of 40ml washing, precipitation obtains 7.5 grams 2,6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenol.
Embodiment 3:2,6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenoxypropanol synthetic
To 40mlN, add 14.8 grams 2 in the dinethylformamide, 6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenol, 4.5 the gram Anhydrous potassium carbonate, Dropwise 5 .0 gram 3-bromopropyl alcohol under the room temperature, room temperature reaction 24 hours, add 100ml water, use the 100ml ethyl acetate extraction again,, obtain 16 grams 2 behind the precipitation through twice washing, 6-two chloro-4-(3 ', 3 '-dichloro) the allyloxy phenoxypropanol.After the purification, structure is confirmed through H-NMR.
2.0 (s, 1H, OH), 2.05-2.20 (m, 2H ,-CH2-), 3.9-4.2 (m, 2H ,-OCH2-), 4.5-4.7 (d.2H ,-OCH2-), 6.0-6.1 (t, 1H ,=CH-), 6.8-7.0 (s``, 2H, phenyl ring).
Embodiment 4: compound (I): 3, and 5-two chloro-4-(3-(N-(4-trifluoro ethoxy phenyl) carbamoyloxy) propoxyl group)-1-(3,3-two chloro-2-allyloxys) benzene synthetic
3.5 the gram solid phosgene is dissolved in the 100ml ethyl acetate, room temperature drips 2.1g to trifluoro ethoxy aniline, and back flow reaction is after 4 hours, precipitation adds 50ml benzene, 0.15 gram triethylamine, add 4 grams 2,6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenoxypropanol room temperature reaction 10 hours, through layering, the 100ml washing, organic layer obtains 5.9 through the decompression precipitation and digests compound (I) crude product, and chromatography (ethyl acetate: n-hexane=2: 1) after the purification, confirm through H-NMR by structure.
Embodiment 5: compound (II): 3-[3-[2,6-two chloro-4-[(3,3-two chloro-2-pi-allyls) the oxygen base] phenoxy group] propoxyl group] carbonyl-2,7-dimethyl benzofuran synthetic
3.8 restrain 2,6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenol is dissolved in 20mlN, in the dinethylformamide, add 2.9 gram Anhydrous potassium carbonates, 15 ℃ drip 10ml dibromopropane-N down, dinethylformamide solution (dibromopropane-N, the dinethylformamide solution manufacturing method: 4.2 gram dibromopropanes are dissolved in 10mlN, in the dinethylformamide), drip off back room temperature reaction 1 hour, add 3 gram benzofurancarboxylic acids again, reaction is 6 hours under the room temperature, adds 100ml water, use the 100ml ethyl acetate extraction again, through twice washing, precipitation obtains 8 crude products that digest compound (II), chromatography (ethyl acetate: n-hexane=2: 1) confirm through H-NMR, and normal temperature is yellow liquid down by purification back structure.
Embodiment 6: compound (III): 5-[3-[2,6-two chloro-4-[(3,3-two chloro-2-pi-allyls) the oxygen base] phenoxy group] acylamino-]-2,2-dimethyl benzofuran synthetic
6 gram solid phosgenes are dissolved in the 80ml ethyl acetate, 15 ℃ drip 20ml benzofuran amine-ethyl acetate solution (benzofuran amine-ethyl acetate solution preparation method: 3.3 gram benzofuran amine are dissolved in the 20ml ethyl acetate solution) down, after the back flow reaction 1 hour, precipitation, add 80ml benzene, 8 grams 2,6-two chloro-4-(3 ', 3 '-dichloro) the allyloxy phenoxypropanol, 0.3 the gram triethylamine, room temperature reaction 20 hours is through layering, washing, obtain compound (III) behind the precipitation, crude product 10.5 grams, chromatography (ethyl acetate: n-hexane=2: 1) after the purification, structure confirms that through H-NMR normal temperature is brown liquid down.
Embodiment 7: compound (IV): 3-[3-[2,6-two chloro-4-[(3,3-two chloro-2-pi-allyls) the oxygen base] phenoxy group] the third oxygen carbonyl]-2-chloropyridine synthetic
1.9 restrain 2,6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenol is dissolved in 10mlN, and in the dinethylformamide, add 1.5 gram Anhydrous potassium carbonates and drip 10ml dibromopropane-N down for 15 ℃, dinethylformamide solution (dibromopropane-N, the dinethylformamide solution manufacturing method: 2.1 gram dibromopropanes are dissolved in 10mlN, dinethylformamide solution), drip off back room temperature reaction 1 hour, in above-mentioned solution, add 50mlN, dinethylformamide, 0.35 gram 2-chlorine apellagrin, 0.4 gram Anhydrous potassium carbonate, reaction is 5 hours under the room temperature, add 100ml water, use the 100ml ethyl acetate extraction again, through layering, washing obtains compound (IV) crude product 0.3 gram behind the precipitation.(ethyl acetate: n-hexane=2: 1) after the purification, structure confirms that through H-NMR normal temperature is yellow liquid down to chromatography.
Embodiment 8: compound (V): 2-[3-[2,6-two chloro-4-[(3,3-two chloro-2-pi-allyls) the oxygen base] phenoxy group] propoxyl group]-5-chloropyridine synthetic
In the 30ml n-hexane, add 3.4 grams 2,6-two chloro-4-(3 ', 3 '-dichloro) the allyloxy phenoxypropanol, 1 gram 2, the 5-dichloropyridine, be heated to backflow, drip 1.2 grams, 50% sodium hydroxide solution, the waterside back flow reaction is divided on the limit then, after 7 hours, through layering, washing obtains compound (V) crude product 3.7 grams behind the precipitation.(ethyl acetate: n-hexane=2: 1) structure is confirmed through H-NMR, and normal temperature is yellow liquid down through the chromatography purification.
Embodiment 9: compound (VI): 3,5-two chloro-[4-[3-(2,2,3, the 3-tetramethyl) cyclopropyl] carbonyl propoxyl group]-1-(3,3-two chloro-2-pi-allyls) oxygen base) benzene synthetic
To 20ml N, add 4.2 grams 1 in the dinethylformamide, the 3-dibromopropane, 2.9 the gram Anhydrous potassium carbonate is dissolved with 3.8 grams 2,6-two chloro-4-(3 ' to wherein dripping again, 3 '-dichloro) 10mlN of allyloxy phenol, dinethylformamide solution is controlled temperature about 15 ℃, and reacts 30 minutes under this temperature, add 2.9 gram chrysanthemumic acid then, reaction is 22 hours under the room temperature, adds 100ml water, uses the 100ml ethyl acetate extraction again, through twice washing, precipitation obtains compound (VI) crude product 8.3 grams, and chromatography (ethyl acetate: n-hexane=2: 1) after the purification, confirm through H-NMR by structure.
Embodiment 10: compound (VII): 2-[3-[2,6-two chloro-4-[(3,3-two chloro-2-pi-allyls) the oxygen base] phenoxy group] propoxyl group] anthraquinone synthetic
In the 20mL n-hexane, add 2 grams 2,6-two chloro-4-(3 ', 3 '-dichloro) the allyloxy phenoxypropanol, 1.1 gram 2-chloroquinolines drip 1.0 grams, 50% sodium hydroxide solution, backflow also divides water reaction 10 hours, layering, organic layer is washed through 100ml, and the oil reservoir precipitation that reduces pressure is obtained compound (VII) crude product 3.3 gram, chromatography (ethyl acetate: n-hexane=2: 1) after the purification, confirm through H-NMR by structure.
Embodiment 11: compound (VIII) 5-[3-[2,6-two chloro-4-[(3,3-two chloro-2-pi-allyls) the oxygen base] phenoxy group] propoxyl group]-2-methyl benzofuran synthetic
To 30ml N, add 2.1 grams 1 in the dinethylformamide, the 3-dibromopropane, 1.5 gram Anhydrous potassium carbonates are dissolved with 1.9 grams 2 to wherein dripping again, 6-two chloro-4-(3 ', 3 '-dichloro) 10mlN of allyloxy phenol, dinethylformamide solution, the control temperature is about 15 ℃, and under this temperature, reacted 30 minutes, add 1.5 gram p-aminophenyl and furans then, reaction is 24 hours under the room temperature, adds 100ml water, use the 100ml ethyl acetate extraction again, through layering, washing obtains compound (VIII) crude product 4.3 grams behind the precipitation, chromatography (ethyl acetate: n-hexane=2: 1) after the purification, confirm through H-NMR by structure.
Embodiment 12: compound (IX): 2-[3-[2,6-two chloro-4-[(3,3-two chloro-2-pi-allyls) the oxygen base] phenoxy group] propoxyl group]-7,7-dimethyl benzofuran synthetic
In 100ml methyl alcohol, add catechol 11.1 grams, methylallyl chloride 9.2 grams, Anhydrous potassium carbonate 10.5 grams, be heated to 40 ℃ of reactions 6 hours, add 100ml water, use the 100ml ethyl acetate extraction again, through layering, washing obtains 2-allyloxy phenol 7.3 grams behind the precipitation.
The said goods is heated to 190 ℃ of reactions 1 hour, is cooled to then below 100 ℃, add dimethylbenzene 150ml, p-methyl benzenesulfonic acid 4.3 grams, back flow reaction 3 hours obtains benzofuran phenol after routine is handled, 5.4 grams.
To 20ml N, add 4.2 grams 1 in the dinethylformamide, 3-dibromopropane, 2.9 gram Anhydrous potassium carbonates, be dissolved with 3.8 grams 2 to wherein dripping again, the 10mlN of 6-two chloro-4-(3 ', 3 '-dichloro) allyloxy phenol, dinethylformamide solution, the control temperature is about 15 ℃, and under this temperature, reacted 30 minutes, add 0.6 gram benzofuran phenol, 0.57 gram Anhydrous potassium carbonate, reaction is 30 hours under the room temperature, add 100ml water, use the 100ml ethyl acetate extraction again, through layering, washing, obtain compound (IX) crude product 1.85 grams behind the precipitation, chromatography (ethyl acetate: n-hexane=2: 1) after the purification, confirm through H-NMR by structure.Normal temperature is white paste solid down.

Claims (1)

1. dichloropropylene type pesticide is characterized in that this insecticide has following general structure (A):
Figure C2006100465680002C1
Ar is 5-chloropyridine base or anthraquinonyl in the formula.
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JP4904947B2 (en) 2006-07-04 2012-03-28 住友化学株式会社 Method for producing alcohol compound
CN101747306B (en) * 2008-11-28 2012-08-29 中国中化股份有限公司 Substituent ether compound and application thereof
CN101863851B (en) * 2009-04-14 2011-12-21 中国中化股份有限公司 Dichloropropylene compound and application thereof
CN101863828B (en) * 2009-04-14 2012-01-11 中国中化股份有限公司 3, 5, 6-three-halogenated pyridyl ethers compound and application thereof
CN102718701B (en) 2011-03-30 2014-05-07 中国中化股份有限公司 Aryloxy dihalide propylene ether compound and application thereof
CN104974083B (en) * 2014-04-04 2017-12-15 华中师范大学 Dichloro allyl ether series compound, insecticide and its application
CN107279147A (en) * 2017-08-17 2017-10-24 江西正邦生物化工有限责任公司 A kind of composition pesticide containing pyridalyl

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