CN1491559A - Fly expelling line incense - Google Patents
Fly expelling line incense Download PDFInfo
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- CN1491559A CN1491559A CNA03154441XA CN03154441A CN1491559A CN 1491559 A CN1491559 A CN 1491559A CN A03154441X A CNA03154441X A CN A03154441XA CN 03154441 A CN03154441 A CN 03154441A CN 1491559 A CN1491559 A CN 1491559A
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- joss stick
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Abstract
Provided is a practical fly repellant incense excellent in vaporization rate and insecticidal effect when smoking. This fly repellant incense is obtained by blending 5-propagyl-2-furylmethyl(+)-cis, trans-chrysanthemate, 0.1-1.0 wt. % of 1 kind or >=2 kinds selected from fluorine-substituted benzyl alcohol ester compounds expressed by formula (I) (wherein, R<SB>1</SB>is H or methyl, and when the R<SB>1</SB>is H, R<SB>2</SB>is 3-methoxy-3-oxo-1-propenyl, and when the R<SB>1</SB>is methyl, R<SB>2</SB>is also methyl; and X is H, F, methoxymethyl or propagyl) as active ingredients and preferably further 1 kind or >=2 kinds of di-tertiary butylphenol-based stabilizers each having >=250[deg.]C boiling point.
Description
Technical field
The present invention relates to the improvement of Shoofly joss stick.
Background technology
Smoke mosquito-repellent incense, the insecticide of using as the adult of driving away mosquito, just looked in the past as far back as 100 years by the parent, as its active ingredient, (±)-2-pi-allyl-3-methyl-ring penta-2-alkene-1-ketone-4-base (+)-suitable, instead-chrysanthemum monocarboxylate (finishing that life (ピ Na ミ Application Off オ Le テ) (Pynaminforte)) and stereoisomer thereof hereinafter referred to as brute force, for example エ ス バ イ オ ス リ Application (Esbiothrin) and エ ス PVC オ Le chrysanthemum monocarboxylate compounds such as (Esbiol), because its heating evaporation and heat endurance just are widely used now.On the other hand, for fly, though occur to reduce in the city, in the fishing village, aquatic product manufactory, destructor plant and peripheries such as animal house, hen house are vexing all the time.Produce the countermeasure in source as fly, except using insecticides such as emulsion, finish, pulvis, general family generally uses and drives away the aerosol that adult is used, and is the shortcoming of disposable shortage continuation effect but there is what is called.Therefore, wish a kind of Shoofly joss stick of exploitation, promptly as the spatial manipulation agent, and effect continues a few hours, even and then diffusibility to get well in open place also effectively line spices type.
Smoke mosquito-repellent incense for use a match can keep spatial manipulation for a long time, until after-flame, render a service stable, very rational desinsection mode.The active ingredient that smokes mosquito-repellent incense is near the position volatilization of counting apart from combustion parts 200～250 ℃ of mm, and this temperature is compared with the heater temperature (120～170 ℃) of electric mosquito repellent and will be exceeded a few minutes.Even knownly do not add stabilizing agent in containing the powerful line spices of finishing that life at present, the volatility of active ingredient also can reach 60～80%, but a little less than the effectiveness for fly, even improve the active ingredient concentration in the line spices, also is difficult to be applicable to Shoofly joss stick.
Present inventors select vapour pressure is the highest in the commercially available pyrethroid Prallethrin (Empenthrin) as active ingredient, developed the Shoofly joss stick (No. 3001169 communique of patent) that contains it, but it is not only unfavorable on the cost, and volatility is too high, and loss is arranged in the drying process during fabrication unavoidably.Therefore, the active ingredient of selected the most suitable Shoofly joss stick is an important problem, for example open and disclose in the flat 10-203905 communique with 2-pi-allyl-3-methyl-ring penta-2-alkene-1-ketone-4-base-2 the spy, 2,3, the 3-4-methyl cyclopropane carboxylic acid ester may not be gratifying product still as the Shoofly joss stick of active ingredient.
No. 3001169 communique of patent documentation 1 patent
Patent documentation 2 spies open flat 10-203905 communique
Summary of the invention
The objective of the invention is to the line spices form, select to also have mosquito to have the active ingredient of higher insecticidal effect certainly, the useful Shoofly joss stick that contains this composition is provided than complete those life line spices of present brute force for fly.
In order to solve above-mentioned problem, present inventors are conceived to 5-propargyl-2-furfuryl (+)-suitable, instead-compound of chrysanthemum monocarboxylate (hereinafter referred to as the d-PH) and general formula (I) expression render a service with respect to the desinsection of fly and vapour pressure above-mentioned Prallethrin and powerful finishing between that life, attempted the compound of general formula (I) expression is used for Shoofly joss stick.Also have, the compound of general formula (I) expression is opened in clear 57-165343 communique, special public clear 62-48660 communique and the special fair 7-29989 communique the spy and is disclosed, though wherein put down in writing the embodiment that smokes mosquito-repellent incense, the technical conceive of relevant Shoofly joss stick is not narration a bit.And the Shoofly joss stick of finding to contain above-claimed cpd shows that the high fly that kills renders a service, and is not only favourable on the cost, and the volatility of the appropriateness that compound had can not produce the loss when making, and has high diffusibility when line spices use.
In addition, present inventors are in order to improve the volatile performance of above-claimed cpd, when the various stabilizing agent of research, find by to mix a kind or 2 kinds or above boiling point with respect to 0.1～2.0 times of amount of above-mentioned active ingredient at 250 ℃ or above di-t-butyl-phenol stabilizing agent, not only the stability when ageing stability but also fumigation also significantly strengthens, raising for volatile performance has contribution, thereby has finished the present invention.
That is, the present invention adopts following formation.(1) a kind of rope yarn perfume (or spice) that drives contains 0.1～1.0 weight % and is selected from d-PH and general formula (I)
[changing 1]
(in the formula, R
1For hydrogen atom or methyl, work as R
1During for hydrogen atom, R
2Expression 3-methoxyl group-3-oxo-1-acrylic is worked as R
1When being methyl, R
2Also represent methyl.In addition, X represents hydrogen atom, fluorine atom, methoxy or propargyl.) in the benzyl alcohol ester compounds that replaces of the fluorine of expression a kind or 2 kinds or above as active ingredient.
(2) Shoofly joss stick of record, wherein R in general formula (I) in (1)
1Be hydrogen atom, R
2In the benzyl alcohol ester compounds that replaces for the fluorine of 3-methoxyl group-3-oxo-1-acrylic, the cyclopropane carboxylic acid acid moieties is 1R, and cis-structure, two keys have the Z configuration.
(3) Shoofly joss stick of record in (1) or (2), wherein with a kind or 2 kinds or above boiling point at the di-t-butyl more than 250 ℃-phenol stabilizing agent, with respect to 0.1～2.0 times of amount of above-mentioned active ingredient with effectively fully be mixed together.
The present invention selects the compound of a kind or 2 kinds or the above d-of being selected from PH and general formula (I) as active ingredient, preferably by mixing with specific stabilizing agent, provides volatility and desinsection when smoking cigarette to render a service extremely excellent and practical Shoofly joss stick.
Embodiment
In the present invention, except the d-PH, also use the compound of general formula (I) as active ingredient.If the compound of illustration general formula (I) is then as follows.Compound (A): 2,3,5,6-ptfe benzyl-2,2-dimethyl-3-(3-methoxyl group-3-oxo-1-acrylic) cyclopropanecarboxylcompound,
Compound (B): 2,3,4,5,6-PFBBR-2,2-dimethyl-3-(3-methoxyl group-3-oxo-1-acrylic) cyclopropanecarboxylcompound,
Compound (C): 4-methoxy-2,3,5,6-ptfe benzyl-2,2-dimethyl-3-(3-methoxyl group-3-oxo-1-acrylic) cyclopropanecarboxylcompound,
Compound (D): 4-propargyl-2,3,5,6-ptfe benzyl-2,2-dimethyl-3-(3-methoxyl group-3-oxo-1-acrylic) cyclopropanecarboxylcompound.
In these compounds, asymmetric carbon and two key based on the cyclopropane carboxylic acid acid moieties, there is stereoisomer, any all comprising in the present invention in various active body, racemic modification, any mixture, but preferred cyclopropane carboxylic acid acid moieties is 1R, cis-structure, two keys have the stereoisomer of Z configuration.
Compound (E): 2,3,5,6-ptfe benzyl-2,2,3, the 3-4-methyl cyclopropane carboxylic acid ester,
Compound (F): 2,3,4,5,6-PFBBR-2,2,3, the 3-4-methyl cyclopropane carboxylic acid ester,
Compound (G): 4-methoxy-2,3,5,6-ptfe benzyl-2,2,3, the 3-4-methyl cyclopropane carboxylic acid ester,
Compound (H): 4-propargyl-2,3,5,6-ptfe benzyl-2,2,3,3-4-methyl cyclopropane carboxylic acid ester.
Also have, in compound (E) or compound (H), do not have stereoisomer.
Above-claimed cpd is compared for fly with complete that life of brute force has higher desinsection effectiveness, mixes with 0.1～1.0 weight %, preferred 0.2～0.9 weight % in Shoofly joss stick.If less than 0.1 weight % then can not get desirable insecticidal effect, mix even surpass 1.0 weight % on the other hand, can not confirm to render a service especially enhancing.
In addition, in above-claimed cpd, can certainly suitably mix existing pyrethroid, for example, Bi Naming (ピ Na ミ Application), powerful that life, bioallethrin (Bioallethrin), エ ス バ イ オ ス リ Application (Esbiothrin), エ ス PVC オ Le (Esbiol), prallethrin (Prallethrin), Prallethrin (Empenthrin) or the transfluthrin (Transfluthrin) etc. finished.
Shoofly joss stick of the present invention is characterised in that the compound of selected d-PH and general formula (I), preferably mixes boiling point at 250 ℃ or above di-t-butyl-phenol stabilizing agent as stabilizing agent.For example, a tert-butyl phenol stabilizing agent of 3-t-Butyl-4-hydroxyanisole and 2-tertiary butyl-4-hydroxy methyl phenyl ethers anisole and so on does not have effect, in addition for N, and the amine stabilizing agent of N-diphenyl-p-phenylenediamine (PPD) and Phenyl beta naphthylamine and so on, effect is also low.In addition, boiling point can think that 250 ℃ or the above effective reason of material because the active ingredient pyrethroid volatilizees, this is non-volatile under this temperature and require stabilizing agent near 200～250 ℃.
As the stabilizing agent that uses among the present invention, can be listed below, but be not limited to these.
Stabilizing agent A:2,6-di-tert-butyl-4-methy phenol (BHT),
Stabilizing agent B:2,2-methylene two (4-methyl-6-tert butyl phenol),
Stabilizing agent C:2,2-methylene two (4-ethyl-6-tert-butyl phenol),
Stabilizing agent D:4,4-butylidene two (3 methy 6 tert butyl phenol),
Stabilizing agent E:4,4-sulfo-two (3 methy 6 tert butyl phenol),
The stabilizing agent F:2-tert-butyl group-6-(3-weighs butyl-2-hydroxy-5-methyl-benzyl)-4-aminomethyl phenyl acrylate,
Stabilizing agent G:2,4-di-t-butyl-butyl phenyl-3,5-di-tert-butyl-4-hydroxybenzoic acid ester.
Also have, 1 kind or 2 kinds or above aforementioned stable agent in the present invention, with the compound with respect to a kind or 2 kinds or the above d-of being selected from PH and general formula (I) is that 0.1～2.0 times of amount is mixed, but can certainly be to existing various stabilizing agents such as mixed phosphate ester class, amine, organic sulfur class wherein.
Shoofly joss stick of the present invention in above-mentioned active ingredient composition, can add Butacide, MGK-2 64, MGK-5 026, S-421, リ-synergist such as セ Application 384 if desired.In addition, also can suitably add Dalmatian chrysanthemum and extract combustion adjuvants such as dregs of rice powder, wood powder, pastes such as nanmu tree powder ( Block powder), starch, dextrin, gum Arabic, CMC, as the malachite green of colouring agent with as the dehydroactic acid and 2 of mould inhibitor, 2, 4-dinitrophenol, in addition can also suitably add mineral micropowder, polyethylene glycol etc., can prepare Shoofly joss stick according to conventional method.
According to the present invention, compound by selecting d-PH and general formula (I) is as active ingredient, the effect of preferably mixing specified stabiliser, finish the higher insecticidal effect of those life line spices even also can reach than existing brute force for mosquito for fly certainly, exceedingly useful Shoofly joss stick can be provided.
Enumerate test example and embodiment below and illustrate in greater detail the present invention, but only otherwise exceed aim of the present invention, then not only be confined to these.
Embodiment 1
Use the prescription modulation Shoofly joss stick shown in the following table, the volatility of active ingredient when research smokes cigarette, render a service for the desinsection of fly adult.Also have,, except the composition of record, also add 20 weight % starch, 0.2 weight % dehydro sodium acetate, 15 weight % Dalmatian chrysanthemums extraction dregs of rice powder and wood powder, make that total amount is 100 weight % for other compositions.In addition, to render a service be to be that the relative effectivenes of 1.0 down effect is represented with the powerful line spices of finishing that life of 1.2 weight % to desinsection.
Table 1
| Prescription (weight %) | Active ingredient volatility (%) | Desinsection is renderd a service | |||||
| Active ingredient | Stabilizing agent | ||||||
| The present invention | ?1 ?2 ?3 ?4 ?5 ?6 ?7 ? ?8 ?9 ? ?10 ?11 ?12 ?13 | Powerful that life d-PH compound (F) compound (G) compound (H) of finishing of compound (A) " " " compound (B) " compound (C) compound (D) compound (C) | ?0.1 ?0.4 ?0.4 ?1.0 ?0.2 ?0.7 ?0.5 ? ?0.3 ?0.2 ?0.6 ?0.8 ?0.4 ?0.3 ?0.5 | ??- ??- ??A ??B ??C ??- ??D ??G ??A ??- ? ??A ??B ??A ??C | ? ? ??0.6 ??0.5 ??0.2 ? ??0.3 ??0.1 ??0.5 ? ? ??0.6 ??0.3 ??0.1 ??0.2 | ??68 ??71 ??82 ??79 ??77 ??73 ??83 ? ??80 ??72 ? ??79 ??80 ??78 ??77 | ??2.6 ??3.1 ??3.8 ??4.6 ??3.5 ??1.2 ??3.9 ? ??3.7 ??3.4 ? ??3.4 ??3.3 ??4.5 ??4.0 |
| Comparative example | ??1 ??2 ??3 ??4 ??5 ??6 | Powerful that life " " that finishes of compound (A) Prallethrin control compound P* | ?0.05 ?1.2 ?1.3 ?1.2 ?1.2 ?2.4 | ??- ??A ??A ??- ??A ??A | ??0.4 ??0.5 ? ??0.4 ??0.4 | ??67 ??74 ??75 ??67 ??69 ??68 | ??0.7 ??2.2 ??2.3 ??1.0 ??1.0 ??1.1 |
* the spy opens the disclosed 2-pi-allyl of flat 10-203905 communique-3-methyl-ring penta-2-alkene-1-ketone-4-base-2,2,3,3-4-methyl cyclopropane carboxylic acid ester
The result of test, can confirm to contain the Shoofly joss stick of d-PH or general formula (I) compound, preferably by to wherein with respect to 0.1 times of above-claimed cpd amount or above mixing di-t-butyl-butyl-phenol stabilizing agent, improve the volatility of active ingredient when smoking cigarette and finish those life line spices (contrast line spices) with brute force and compare and demonstrate higher desinsection and render a service.
Relative therewith, generally drive away insecticide that fly uses and drive away the insecticide that mosquito uses and compare the dose that needs high concentration.For example, as comparative example 2 and comparative example 3, Prallethrin and control compound P are useful as the active ingredient of Shoofly joss stick, but are necessary for high concentration, so may not be gratifying product.In addition, for containing the powerful Shoofly joss stick of finishing that life, as shown in comparative example 4～6, even improve dose again, also can strengthen hardly the desinsection of fly is renderd a service, but under the situation of the compd A that uses general formula (I), can confirm that dose is relevant with desinsection effectiveness in the scope of 0.1～1.0 weight %, the physicochemical property of compound (particularly vapour pressure) is suitable for Shoofly joss stick.In addition, finish the effect that does not almost have mixed stabilizer in those life line spices in brute force, Shoofly joss stick of the present invention relatively therewith can provide insecticidal activity better line spices by mixing specific stabilizing agent, and its practicality is also high.
Embodiment 2
0.4 part of compound (A) and 0.3 part of stabilizing agent A (2,6 di tert butyl 4 methyl phenol) are evenly mixed with the base material that line spices such as 99.3 parts of Dalmatian chrysanthemums extraction dregs of rice powder, wood powder, starch are used, obtain Shoofly joss stick according to known method.One volume (13g) such line spices use in the room of 6 tatamis, and the volatility of measuring active ingredient is 79%, through 7 and a half hours smoke the cigarette time, can prevent and kill off fly and mosquito fully.
Embodiment 3
Use 0.25 part of compound (B), 0.2 part of transfluthrin, the 0.1 part of stabilizing agent F[2-tert-butyl group-6-(the 3-tert-butyl group-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate] and 0.3 part of MGK-264, make Shoofly joss stick according to embodiment 2.Shoofly joss stick is put into the line spices container of suspension, reduce under the waist produce most flies animal house in operate, through about 6 hours, the worry of being brought by fly did not have.
Embodiment 4
Use 0.8 part of d-PH, 0.6 part of stabilizing agent A (2,6 di tert butyl 4 methyl phenol), make Shoofly joss stick according to embodiment 2.When near the many houses of piggery fly intrusion, using, do not find the fly intrusion.
Industrial utilizability
Shoofly joss stick of the present invention because that the volatility when smoking cigarette and desinsection are renderd a service is good, also can be used as and smokes the mosquito line spices and use and extremely practical, and therefore the development for the pesticide process industry will contribute.
Claims (3)
1. Shoofly joss stick is characterized in that containing 0.1～1.0 weight % and is selected from 5-propargyl-2-furfuryl (+)-suitable, anti--chrysanthemum monocarboxylate and general formula (I)
[changing 1]
(in the formula, R
1For hydrogen atom or methyl, work as R
1During for hydrogen atom, R
2Expression 3-methoxyl group-3-oxo-1-acrylic is worked as R
1When being methyl, R
2Also represent methyl.In addition, X represents hydrogen atom, fluorine atom, methoxy or propargyl.) in the benzyl alcohol ester compounds that replaces of the fluorine of expression a kind or 2 kinds or above as active ingredient.
2. the Shoofly joss stick of record in the claim 1 is characterised in that the R at general formula (I)
1Be hydrogen atom, R
2In the benzyl alcohol ester compounds that replaces for the fluorine of 3-methoxyl group-3-oxo-1-acrylic, the cyclopropane carboxylic acid acid moieties is 1R, and cis-structure, two keys have the Z configuration.
3. the Shoofly joss stick of record in the claim 1 or 2 is characterised in that a kind or 2 kinds or above boiling point at 250 ℃ or above di-t-butyl-phenol stabilizing agent, with respect to 0.1～2.0 times of amount of above-mentioned active ingredient with effectively fully be mixed together.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002289618 | 2002-10-02 | ||
| JP289618/2002 | 2002-10-02 | ||
| JP2003315524A JP2004143151A (en) | 2002-10-02 | 2003-09-08 | Fly repellant incense |
| JP315524/2003 | 2003-09-08 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101438377A Division CN100539845C (en) | 2002-10-02 | 2003-09-28 | Fly and mosquito-repellent incense |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1491559A true CN1491559A (en) | 2004-04-28 |
| CN100482076C CN100482076C (en) | 2009-04-29 |
Family
ID=32473367
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB03154441XA Expired - Fee Related CN100482076C (en) | 2002-10-02 | 2003-09-28 | Fly expelling line incense |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2004143151A (en) |
| CN (1) | CN100482076C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101524084B (en) * | 2009-04-30 | 2012-11-07 | 江苏扬农化工股份有限公司 | Muscicide incense and preparation method and application thereof |
| CN101467528B (en) * | 2007-12-27 | 2014-06-04 | 大日本除虫菊株式会社 | Incense stick for expelling mosquito or fly |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006256991A (en) * | 2005-03-16 | 2006-09-28 | Sumitomo Chemical Co Ltd | Method for producing insecticidal incense stick and insecticidal incense stick |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0060617A1 (en) * | 1981-03-18 | 1982-09-22 | Imperial Chemical Industries Plc | Fluorobenzyl cyclopropane carboxylates, their preparation, compositions and use as insecticides |
| GB8505819D0 (en) * | 1985-03-06 | 1985-04-11 | Ici Plc | Fluorobenzyl esters |
| FR2610624B1 (en) * | 1987-02-06 | 1989-06-09 | Roussel Uclaf | NOVEL ESTERS OF PYRETHRIC ACID-LIKE CYCLOPROPANECARBOXYLIC ACIDS, THEIR PREPARATION PROCESS AND THEIR APPLICATION TO PEST CONTROL |
| JP2001316212A (en) * | 1999-06-30 | 2001-11-13 | Dainippon Jochugiku Co Ltd | Method for thermal transpiring to kill insect |
-
2003
- 2003-09-08 JP JP2003315524A patent/JP2004143151A/en active Pending
- 2003-09-28 CN CNB03154441XA patent/CN100482076C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101467528B (en) * | 2007-12-27 | 2014-06-04 | 大日本除虫菊株式会社 | Incense stick for expelling mosquito or fly |
| CN101524084B (en) * | 2009-04-30 | 2012-11-07 | 江苏扬农化工股份有限公司 | Muscicide incense and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004143151A (en) | 2004-05-20 |
| CN100482076C (en) | 2009-04-29 |
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Granted publication date: 20090429 Termination date: 20170928 |