CN1092762A - Novel pyrethroid---efficient pyrethroid - Google Patents
Novel pyrethroid---efficient pyrethroid Download PDFInfo
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- CN1092762A CN1092762A CN 93112374 CN93112374A CN1092762A CN 1092762 A CN1092762 A CN 1092762A CN 93112374 CN93112374 CN 93112374 CN 93112374 A CN93112374 A CN 93112374A CN 1092762 A CN1092762 A CN 1092762A
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Abstract
A kind of novel pyrethroid, its chemical name be (R, S)-(E)-cyclopropane-carboxylic acid-3-(2,2)-dichloroethylene-2, the 2-dimethyl-(R, S)-(E Z)-1-cyano group-2-methyl-2-amylene ester, abbreviates trans pyrethroid as.Its activity is much higher than mixture, and synthetic method is simple, and is with low cost, and is that the trans-chrysanthemate of separating in the high-cis Cypermethrin has found outlet.
Description
The invention belongs to the agricultural chemical insecticide class.
Since first pyrethroid-esbiothrin in 1949 comes out, the R and D of pyrethroid insecticides are progress day by day worldwide, wherein kills chrysanthemum ester, Permanone, Cypermethrin, Deltamethrin turnout for bigger with what sprinkling on agricultural and the health prevented and treated usefulness.But it is because the molecular weight of above-mentioned these pyrethroids is bigger, not volatile, so all not satisfactory in the effect that is used for aspect the mosquito-repellent incense fumigation.The higher esbiothrin fumigation effect of another kind of vapour pressure is better, complex structure, and synthetic difficulty is big, though domestic have production, but higher because of cost, have only on a small scale and go into operation.
Another kind of in recent years pyrethroid-pyrethroid begins to be gazed at (the special clear 54-136821 of hope) (Tap.J.Sahit.Zool.Vol.34 NO.4 P263-268 1983) by people.The authors etc. also once did research to this, found that it all is better than above-mentioned other class pyrethroids at aspects such as result of use, synthetic difficulty, Financial cost, and had the prospect of further exploitation.(the 8th phase of chemistry world P348-350 1986)
The objective of the invention is to further research and develop this class pyrethroid, bigger to obtain activity, effect is better, and the outstanding compound that cost is lower is further realized large-scale industrial production then.
Efficient pyrethroid of the present invention is a kind of novel pyrethroid, is a kind of trans-isomer(ide) of pyrethroid.Chemical name is (R, S)-(E)-cyclopropane-carboxylic acid-3-(2,2-dichloroethylene)-2, the 2-dimethyl-(R, S)-(E, Z)-1-cyano group-2-methyl-2-amylene ester, abbreviate trans pyrethroid as.Its structural formula is as follows:
Molecular formula: C
15H
19Cl
2NO
2
Molecular weight: 316
Ultimate analysis: calculated value % C56.95 H6.06 N4.43
Measured value % C57.13 H6.46 N4.23
Proterties: little yellow transparent liquid
Proportion: D
20=1.08
Boiling point: 150-152 ℃/0.3mmHg
Refractive index: n
20 D=1.5000
n
13 D＝1.5022
Molten Jie's degree: be soluble in organic solvents such as ethanol, be insoluble in water.
Infrared spectra: (cm
-1)
2250，1740，1610，1180，890，650
Nucleus magnetic resonance: (CDCl
3TMS δ PPM)
δ??0.8-1.4??10H??δ1.6-2.4??7H??δ??5.6??1H??δ??5.7??1H
Efficient pyrethroid of the present invention can be prepared by following method.
The present invention is a raw material with DV chrysanthemumic acid cis-trans-isomer mixture, make high-cis DV chrysanthemumic acid and two kinds of isomer of trans DV chrysanthemumic acid respectively by separating, then trans-isomer(ide) is carried out chloride, to produce trans dichloro chrysanthemum acyl chlorides, again with 2-methylpentene-2-aldehyde and sodium cyanide condensation, finally obtain trans pyrethroid, promptly efficient pyrethroid.
The mixture of DV chrysanthemumic acid cis-trans-isomer can make by the phase mould-Kurarayi method of classics, and its reaction formula is roughly as follows:
The weight ratio of the cis-trans-isomer of the DV chrysanthemumic acid mixture of gained is about about 4: 6.Place organic solvent to be separated in mixture, used solvent can be a cyclohexane, sherwood oil and ether etc.Cis-isomeride mostly is dissolved in the solvent, solid part is filtered, recrystallization get final product the DV chrysanthemumic acid of trans-isomer(ide), its cis can reach 2: 98 with trans ratio.And the high-cis isomer of gained (cis is about 84: 16 with trans ratio) can be directly used in high synthesizing along Cypermethrin.
The chloride of trans DV chrysanthemumic acid can be a chlorizating agent with sulfur oxychloride, in the small amount of toluene solvent behind heating reflux reaction, fraction when 130-133 ℃/50mmHg post is collected in distillation get final product the oily matter of trans dichloro chrysanthemum acyl chlorides, yield and content all can be greater than more than 95%.
2-methylpentene-2-aldehyde as the condensation group can be made by propionic aldehyde dealcoholysis dehydration, and propionic aldehyde can be produced from the propyl alcohol oxidation or by rectifying after the propylene oxide isomerization.Its chemical equation is as follows:
The condensation of trans dichloro chrysanthemum acyl chlorides and 2-methylpentene-2-aldehyde and sodium cyanide need be carried out in the presence of varsol and phase-transfer catalyst, and used varsol can be an alkane, as normal hexane, and cyclohexane etc.; Also can be aromatic hydrocarbons, as benzene, dimethylbenzene etc.Phase-transfer catalyst can be tetraethylammonium bromide, Tetrabutyl amonium bromide, and triethyl benzyl brometo de amonio or etamon chloride etc., its chemical equation is as follows:
Pyrethroid is a low toxicity compounds, the oral acute LD of its small white mouse
50Be 3205mg/kg, than esbiothrin (LD
50Be 480mg/kg) low nearly order of magnitude.The activity of its trans-isomer(ide) is big than cis-isomeride after tested.And be the Permanone and the Cypermethrin of raw material with the DV chrysanthemumic acid equally, be main active ingredient but with cis-isomeride.The ratio of cis-isomeride and trans-isomer(ide) is about 3 in the existing commercially available DV chrysanthemumic acid: 7-4: between 6, like this by separation to the DV chrysanthemumic acid, come the synthesis of trans pyrethroid with its trans-isomerism body portion, and partly be used for synthesizing high-cis Permanone or Cypermethrin with its high-cis isomer, not only can improve the biological activity of above-mentioned various product greatly, strengthen drug effect, and can accomplish to make the best use of everything, to reduce the generation of activity than the product of lower part, thereby will reduce production costs significantly, strengthen the ability of market competition.
The preparation of synthetic example 1 DV chrysanthemumic acid
In that being housed, agitator, condenser, temperature take into account in 500 milliliters of there-necked flasks of water-bath, input cis-isomeride and trans-isomer(ide) are 4: 6 DV chrysanthemumic acid mixtures of methyl esters 78.1 grams (0.35 mol), add 1.8 molar aqueous sodium hydroxide solutions again, heating hydrolysis in 50 milliliters of cyclohexanes.After hydrolysis finished, organic solvent was reclaimed in distillation, and water layer is washed to neutrality then with the acidifying of mineral acid example hydrochloric acid.Adding 150 milliliters of toluene again extracts.Discard water layer, distillation removes desolvates, and raffinate inclines to cooling and obtain the mixture of suitable, trans-isomer(ide) that fusing point is 65～68 ℃ a solid DV chrysanthemumic acid in the still.Through gas chromatographic analysis and nuclear magnetic resonance spectroscopy, cis-isomeride: trans-isomer(ide) is 4: 6, and is consistent with ratio before the saponification hydrolysis.
H NMR：（CDCL
3TMS δppm）
Cis body: 1.2(S.3H-CH
3) 1.35(S.3H-CH
3) 1.83(d.1H-CHCOO-)
2.03（t.1H＝
）6.09（d.1H＝
）10.84（b.1H-COOH）
Trans body: 1.21(S.3H-CH
3) 1.35(S.3H-CH
3) 1.61(d.1H-CHCOO-)
2.25（dd.1H
）5.61（d.1H＝
）10.84（b.1H-COOH）
Synthetic example 2 DV chrysanthemumic acid cis-isomerides separate with trans-isomer(ide)
In being housed, 100 milliliters of there-necked flasks of agitator, thermometer add suitable, the trans isomer mixture (cis-isomeride: trans-isomer(ide)=4: 6 weight ratios) of DV chrysanthemumic acid, add an amount of cyclohexane again, under agitation make solid DV chrysanthemumic acid dissolving nearly half, the cis body mostly is dissolved in the solvent, and contains more trans-isomer(ide) in the residual solid.The solid of filtration residue, filter cake carries out recrystallization, obtains being mainly the DV chrysanthemumic acid of trans-isomer(ide), and fusing point is 93～96 ℃, and content is 98.2%, through gas-chromatography and nuclear magnetic resonance spectroscopy, cis: trans=2: 98.Merging filtrate, recrystallization mother liquor, distillation removes solvent, promptly obtains the DV chrysanthemumic acid (cis: trans=84: 16) of high-cis, can be directly used in high synthesizing along Cypermethrin.(H
1NMR numerical value is with example 1)
The preparation of synthetic example 3 trans dichloro chrysanthemum acyl chlorides
In 500 milliliters of there-necked flasks that agitator, thermometer, the cool condenser of backflow and water-bath be housed, pack into through trans DV chrysanthemumic acid 29.3 gram (0.14 the mol) (cis-isomerides: trans-isomer(ide)=2: 98) that split, add 60 milliliters of toluene again and make solvent, drop into 17.8 gram (0.15 mol) sulfur oxychlorides, slowly be warming up to backflow.Reflux after 10 hours, steam solvent under normal pressure or decompression, the fraction of 130-133 ℃/50mmHg post is collected in and then underpressure distillation, promptly obtains the trans dichloro chrysanthemum acyl chlorides of oily matter.Content is 98%, and yield is greater than 96%.
Synthesizing of synthetic example 4 2-methylpentene-2-aldehyde
In 100 milliliters of there-necked flasks of agitator, thermometer, reflux exchanger, dropping funnel and water-bath are housed, add 1 milliliter of 0.06N aqueous sodium hydroxide solution, at room temperature drip propionic aldehyde, treat that propionic aldehyde dropwises after, be incubated 1 hour and make reaction and carry out fully.Be poured into standing demix in the separating funnel after the question response liquid cooling but, organic layer water (25ml * 2) washing twice, branch anhydrates, and adds anhydrous sodium sulfate drying, the elimination siccative, 135～140 ℃ fraction is collected in air distillation, is 2-methylpentene-2-aldehyde.Through gas chromatographic analysis content is 97.7%, and yield is 85.9%.
Synthesizing of synthetic example 5 trans pyrethroids
In 100 milliliters of there-necked flasks that agitator, thermometer, the cool condenser of backflow and water-bath are housed, add solid sodium cyanide 25 grams, 10 milliliters in water, 10 milliliters of toluene and tetraethylammonium bromide 0.2 gram respectively, under the water-bath cooling, drip trans DV chrysanthemum acyl chlorides 11.6 gram (cis-isomerides: trans-isomer(ide)=2: 98), and 2-methylpentene-2-aldehyde 5.0 grams, elder generation's room temperature reaction, heat then, constantly take a sample in the reaction process and carry out the gas-chromatography trace analysis, disappearing with 2-methylpentene-2-aldehyde is reaction end.In reaction solution impouring separating funnel, standing demix separates oil reservoir and water layer, oil reservoir water (25ml * 2) washing secondary, combining water layer, use the methylbenzene extraction secondary, remerge oil reservoir, with 25 milliliters of saturated aqueous solution of sodium bicarbonate washings, branch vibration layer, drying, the reduction vaporization desolventizing obtains the trans pyrethroid of product.n
13 D=1.5022, bp=150-152 ℃/0.3mmHg. post, yield are 90.34%, and content is 93.0%(gas chromatographic analysis value).Cis-isomeride: trans-isomer(ide)=2: 98(is through nuclear magnetic resonance measuring), its isomer proportion is identical with the DV chrysanthemumic acid that feeds intake, no suitable, trans isomer conversion phenomenon generation in the reaction process.
Product: ultimate analysis:
Calculated value % C56.95 H6.06 N4.43
Measured value % C57.13 H6.46 N4.23
Infrared spectra: IR(cm
-1) 2,250 1,740 1,610 1,180 890 650
Nucleus magnetic resonance: H
1NMR(CDCl
3TMS δ ppm)
Trans body: δ 0.8-1.4??1H??δ1.6-2.4??7H??δ5.6??1H??δ5.7
(d.1H=
, three carbocyclic rings are trans)
The preparation of synthetic example 6 high-cis dichloro chrysanthemum acyl chlorides
In 500 milliliters of there-necked flasks that agitator, thermometer, reflux exchanger and water-bath be housed, the high-cis DV chrysanthemumic acid that the folding of packing into divides (cis-isomeride: 29.4 grams (0.14 mol) trans-isomer(ide)=84: 16), add 60 milliliters of toluene again, drop into 17.8 gram (0.15 mol) sulfur oxychlorides, be warming up to backflow.After ten hours back flow reaction, under normal pressure, steam solvent, and then underpressure distillation collects 128-133 ℃/50mmHg post fraction, obtain oily product high-cis dichloro chrysanthemum acyl chlorides, yield is 96%, content is 98%.(cis-isomeride: trans-isomer(ide)=84: 16)
Synthesizing of synthetic example 7 high-cis dicyan penta Cyano chrysanthemate
In 100 milliliters of there-necked flasks of agitator, thermometer, reflux exchanger and water-bath are housed, add high-cis dichloro chrysanthemum acyl chlorides 11.6 gram (the cis body: trans body=84: 16), solid sodium cyanide 2.5 grams, 10 milliliters in water, 10 milliliters of toluene, tetraethylammonium bromide 0.2 gram, and 2-methylpentene-2-aldehyde 5.0 restrain, other reactions and post-processing operation are all same entirely with synthetic example 5, obtain the high-cis pyrethroid at last.Yield 90%, content 90%, cis-isomeride: trans-isomer(ide)=84: 16(is through nuclear magnetic resonance spectroscopy).
H
1NMR：（CDCL
3，TMS δppm）
Cis body: δ 0.8-1.4 10H δ 1.6-2.4 7H δ 5.7 1H δ 6.2
(d.1H=
, three carbocyclic ring cis)
Trans body: δ 0.8-1.4 10H δ 1.6-2.4 7H δ 5.6 1H δ 5.7
1H=
, three carbocyclic rings are trans)
IR（cm
-1）
Cis body: 2,250 1,740 1,610 1,180 820 650
Trans body: 2,250 1,740 1,610 1,180 890 650
The pyrethroid sample mosquito that test of pesticide effectiveness example 1 contains different cis-trans-isomer ratios is knocked down test
Sample is splashed into blank mosquito-repellent incense respectively, and making it final concentration is 0.5%, and (φ 20cm puts into 20 of female culex pipiens pollens in h43cm), smokes one minute, pipettes mosquito-repellent incense, observes and knocks down the time, and obtain KT at standard testing garden tube
50Value, in contrast, test-results is as follows with commercially available Samsung mosquito-repellent incense (raw material is powerful that life that finishes of import):
1, Samsung mosquito-repellent incense KT
504 ' 15 "
2, No. 1 KT of agricultural mosquito
505 ' 02 "
3, No. 2 KT of agricultural mosquito
503 ' 14 "
4, No. 3 KT of agricultural mosquito
503 ' 11 "
* wherein: No. 1 (pyrethroid content 90%) (cis: trans=84: 16) of agricultural mosquito
No. 2 (pyrethroid content 90%) (cis: trans=30: 70) of farming mosquito
No. 3 (pyrethroid content 90%) (cis: trans=2: 98) of farming mosquito
The mosquito of test of pesticide effectiveness example 2 efficient pyrethroids and other pyrethroid samples is knocked down test
Evenly be made into sample liquid 3%, drip in blank mosquito-repellent incense, adopt high 43 centimeters, 20 centimeters airtight gardens of diameter tube method of testing.
The mosquito kind: the long-term responsive culex pipiens pollens SEN strain of raising in laboratory, each 20 female mosquitoes are observed and knock down the time, obtain KT
50Value.
Test result is as follows:
No. 3 KT of farming mosquito
502 ' 33 "
No. 4 KT of farming mosquito
502 ' 48 "
No. 5 KT of farming mosquito
504 ' 49 "
* wherein: No. 3 (two Cypermethrin content 90%) (cis: trans=2: 98) of agricultural mosquito
No. 4 (content 89.8%) (Westen and Chinese Tranditional Medicine Pharamacentic Factory mosquito-killing chrysanthemum ester samples) of farming mosquito
No. 5 (content 30%) (no cyano group pyrethroids) of farming mosquito
Claims (6)
1, a kind of novel pyrethroid, its chemical name be (R, S)-(E)-cyclopropane-carboxylic acid-3-(2, the 2-dichloroethylene)-2, the 2-dimethyl-(R, S)-(E, Z)-1-cyano group-2-methyl-2-amylene ester.Be called for short trans pyrethroid.
Structural formula:
2, the preparation method of novel pyrethroid as claimed in claim 1 is characterized in that getting trans dichloro chrysanthemum acyl chlorides by the trans-isomer(ide) that separates DV chrysanthemumic acid mixture gained is carried out chlorination, makes with sodium cyanide and 4.2-methylpentene-2-aldehyde condensation again.
3, the separation of DV chrysanthemumic acid mixture as claimed in claim 2, the solvent that is adopted when it is characterized in that separating is a hexanaphthene.
4, the chlorination of dichlor chrysanthemic acid trans-isomer(ide) as claimed in claim 2 is characterized in that the chlorizating agent that is adopted is a sulfur oxychloride.
5, trans dichloro chrysanthemum acyl chlorides as claimed in claim 2 and sodium cyanide and 4, the condensation of 2-methylpentene-2-aldehyde is characterized in that condensation reaction needs to carry out in the presence of varsol and tetraethylammonium bromide catalyzer.
6, a kind of new and effective hygienic insecticide is characterized in that contained effective ingredient is trans dichloro penta hydrocyanic ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93112374A CN1044807C (en) | 1993-03-23 | 1993-03-23 | Pyrethroid-high-efficiency cypermethrin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93112374A CN1044807C (en) | 1993-03-23 | 1993-03-23 | Pyrethroid-high-efficiency cypermethrin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1092762A true CN1092762A (en) | 1994-09-28 |
| CN1044807C CN1044807C (en) | 1999-08-25 |
Family
ID=4989991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93112374A Expired - Lifetime CN1044807C (en) | 1993-03-23 | 1993-03-23 | Pyrethroid-high-efficiency cypermethrin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1044807C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584592A (en) * | 2011-12-28 | 2012-07-18 | 李进 | Deuterated pyrethroid compound and preparation method and application thereof |
| CN114181079A (en) * | 2020-09-11 | 2022-03-15 | 江苏优嘉植物保护有限公司 | Preparation method of efficient chlorenthrin |
-
1993
- 1993-03-23 CN CN93112374A patent/CN1044807C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584592A (en) * | 2011-12-28 | 2012-07-18 | 李进 | Deuterated pyrethroid compound and preparation method and application thereof |
| CN102584592B (en) * | 2011-12-28 | 2014-10-15 | 李进 | Deuterated pyrethroid compound and preparation method and application thereof |
| CN114181079A (en) * | 2020-09-11 | 2022-03-15 | 江苏优嘉植物保护有限公司 | Preparation method of efficient chlorenthrin |
| CN114181079B (en) * | 2020-09-11 | 2023-10-31 | 江苏优嘉植物保护有限公司 | Preparation method of high-efficiency permethrin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1044807C (en) | 1999-08-25 |
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