NO138429B - INSECT REPRESENTATIVE. - Google Patents
INSECT REPRESENTATIVE. Download PDFInfo
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- NO138429B NO138429B NO367273A NO367273A NO138429B NO 138429 B NO138429 B NO 138429B NO 367273 A NO367273 A NO 367273A NO 367273 A NO367273 A NO 367273A NO 138429 B NO138429 B NO 138429B
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- Prior art keywords
- formula
- insect
- aminopropionic acid
- butyl
- acetyl
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- 241000238631 Hexapoda Species 0.000 title description 10
- 239000000077 insect repellent Substances 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical class NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 claims description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000002537 cosmetic Substances 0.000 claims description 6
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- 239000013543 active substance Substances 0.000 description 15
- 241000255925 Diptera Species 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 8
- 229960001826 dimethylphthalate Drugs 0.000 description 8
- AXMPPCGZGUAUBS-UHFFFAOYSA-N ethyl 2-(hexanoylamino)propanoate Chemical compound CCCCCC(=O)NC(C)C(=O)OCC AXMPPCGZGUAUBS-UHFFFAOYSA-N 0.000 description 8
- 239000004033 plastic Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000005871 repellent Substances 0.000 description 6
- 230000002940 repellent Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 241000283973 Oryctolagus cuniculus Species 0.000 description 4
- 208000002193 Pain Diseases 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 210000000245 forearm Anatomy 0.000 description 4
- 241001465754 Metazoa Species 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 125000004401 m-toluyl group Chemical group [H]C1=C([H])C(=C([H])C(=C1[H])C([H])([H])[H])C(*)=O 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QNAYBMKLOCPYGJ-UHFFFAOYSA-N Alanine Chemical compound CC([NH3+])C([O-])=O QNAYBMKLOCPYGJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 230000005923 long-lasting effect Effects 0.000 description 2
- 210000004400 mucous membrane Anatomy 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LEACJMVNYZDSKR-UHFFFAOYSA-N 2-octyldodecan-1-ol Chemical compound CCCCCCCCCCC(CO)CCCCCCCC LEACJMVNYZDSKR-UHFFFAOYSA-N 0.000 description 1
- 241000256186 Anopheles <genus> Species 0.000 description 1
- 241000256187 Anopheles albimanus Species 0.000 description 1
- ZAKOWWREFLAJOT-CEFNRUSXSA-N D-alpha-tocopherylacetate Chemical compound CC(=O)OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C ZAKOWWREFLAJOT-CEFNRUSXSA-N 0.000 description 1
- MMOXZBCLCQITDF-UHFFFAOYSA-N N,N-diethyl-m-toluamide Chemical compound CCN(CC)C(=O)C1=CC=CC(C)=C1 MMOXZBCLCQITDF-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- -1 carboxylic acid chlorides Chemical class 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical class OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000011874 heated mixture Substances 0.000 description 1
- UFIYKNIUNRVRSI-UHFFFAOYSA-N hexadecyl octadecyl sulfate;sodium Chemical compound [Na].CCCCCCCCCCCCCCCCCCOS(=O)(=O)OCCCCCCCCCCCCCCCC UFIYKNIUNRVRSI-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- GPSDUZXPYCFOSQ-UHFFFAOYSA-N m-toluic acid Chemical compound CC1=CC=CC(C(O)=O)=C1 GPSDUZXPYCFOSQ-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- OULAJFUGPPVRBK-UHFFFAOYSA-N tetratriacontan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO OULAJFUGPPVRBK-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- VLPFTAMPNXLGLX-UHFFFAOYSA-N trioctanoin Chemical compound CCCCCCCC(=O)OCC(OC(=O)CCCCCCC)COC(=O)CCCCCCC VLPFTAMPNXLGLX-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/22—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by carboxyl groups
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/02—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings containing insect repellants
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
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- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Dermatology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Cosmetics (AREA)
- Medicines Containing Plant Substances (AREA)
Description
Foreliggende oppfinnelse angår insektfrastøtende midler The present invention relates to insect repellents
for kosmetiske og tekniske formål, midler som, som aktiv bestand-del, inneholder på nitrogenatomet disubstituerte 3-aminopropionsyrederivater. for cosmetic and technical purposes, agents which, as active ingredient, contain 3-aminopropionic acid derivatives disubstituted on the nitrogen atom.
I motsetning til insekticidene, som hverken hindrer insekter i å slå seg ned eller i å stikke, og som således heller ikke hindrer den eventuelle dermed .forblindede infeksjon, da insekti-cidenes virkning først begynner etter en viss tid, har insekts-beskyttelsesmidler (repellents) den oppgave at de skal hindre skadeinsekter fra å Jiærme seg eller å berøre, og videre fra å stikke og suge i og for seg tillokkende overflater, f.eks. menneskers eller dyrs hud, hvis disse på forhånd er behandlet med disse stoffer. Beskyttelsen fra stikkende, blodsugende og andre ubehagelige insekter er i mange områder et trengende behov, da disse ikke bare er plagsomme for mennesker og husdyr, men også fordi de ofte er istand til å overføre sykdommer. Virksomme stoffer til beskyttelse mot denslags insekter må derfor oppfylle en betydelig sunnhetsmessig, hygienisk og kosmetisk funksjon. In contrast to the insecticides, which neither prevent insects from settling down nor from stinging, and which thus also do not prevent the eventual blinded infection, as the insecticides' effect only begins after a certain time, insect protection agents (repellents) have ) the task that they must prevent harmful insects from touching or touching, and further from stinging and sucking in and for themselves attractive surfaces, e.g. human or animal skin, if these have been previously treated with these substances. Protection from stinging, blood-sucking and other unpleasant insects is an urgent need in many areas, as these are not only troublesome for people and livestock, but also because they are often capable of transmitting diseases. Active substances for protection against such insects must therefore fulfill a significant health, hygienic and cosmetic function.
For beskyttelse av overflater som virker tillokkende på skadelige insekter, ex det allerede foreslått tallrike virksomme stoffer. Spesielt kjent og allerede i lang tid i bruk er.-.: dimetylftalat og m-.toluylsyre-N,N-dietylamid (DEET) . Disse forbindelser har oppnådd en betraktelig betydning som virksomme insektfrastøtende midler i praksis. De kjente og i handelen fore-kommende insektfrastøtende midler har intet felles konstitusjons-prinsipp- For the protection of surfaces that are attractive to harmful insects, numerous active substances have already been proposed. Particularly well-known and already in use for a long time are: dimethyl phthalate and m-toluyl acid-N,N-diethylamide (DEET). These compounds have achieved considerable importance as effective insect repellents in practice. The known and commercially available insect repellents have no common constitutional principle.
En vesentlig mangel ved de k-jente insektfrastøtende midler består J. den -egenskap at de ved dagelig behov beskadiger kunststoffgjenstander ved oppløsning henholdsvis svelling. Ut-over dette har mange av de kjente insektfrastøtende midler ikke, eller kun .1 begrenset grad den for den kosmetiske anvendelse nødvendige og ønskede høye hud— og slimhudfordragelighet. A significant shortcoming of the k-known insect repellents consists in the property that they damage plastic objects when they dissolve or swell when needed on a daily basis. In addition to this, many of the known insect repellents do not, or only to a limited extent, have the necessary and desired high skin and mucosal tolerance for cosmetic use.
Foreliggende oppfinnelse har således til oppgave å utvikle riye insektfrastøtende-midler,som, ved siden av en god og langvarig insektfrastøtende virkning, samtidig har en utmerket for-dragelighet for den menneskelige hud, spesielt slimhinnen, og som ikke angriper og beskadiger kunststoffgjenstander, heller ikke etter lengre kontakt (berøringstid). The present invention thus has the task of developing rich insect repellents, which, in addition to a good and long-lasting insect repellent effect, at the same time have an excellent tolerability for the human skin, especially the mucous membrane, and which do not attack and damage plastic objects, nor after longer contact (contact time).
Det er nå funnet at bestemte, på nitrogenatomet disubstituerte 3-aminopropionsyrederivater (£-alaninderivater) oppviser en meget god og langvarig insektfrastøtende virkning, en høy og de kjente handelspreparater overlegen, hud- og slimhinnefordrage-lighet, og ut over dette har den egenskap at de ikke angriper eller beskadiger kunstoffgjengstander ved de ved anvendelse av insektfrastøtende midler i praksis opptredende betingelser. It has now been found that certain 3-aminopropionic acid derivatives disubstituted on the nitrogen atom (£-alanine derivatives) exhibit a very good and long-lasting insect repellent effect, a high and superior to the known commercial preparations, skin and mucous membrane tolerance, and in addition to this, it has the property that they do not attack or damage plastic objects under the conditions that occur when insect repellents are used in practice.
En sterkt utpreget insektfrastøtende virkning blant de på nitrogenatomet substituerte derivater av 3-aminopropionsyre, er spesielt av den grunn overraskende, fordi den isomere 2—amino-propionsyxe allerede f or mange åer siden er beskrevet som insekt-tillokkende (spesieit tillokkende for stikkmygg) (A.W.A Brown, A.G- Carmichael: "J. Econ. Entomol.", 44, side 317 (1961); B. A strongly pronounced insect-repellent effect among the derivatives of 3-aminopropionic acid substituted on the nitrogen atom is particularly surprising for that reason, because the isomeric 2-amino-propionic acid has already been described many years ago as insect-attractive (especially attractive to biting mosquitoes) ( A.W.A Brown, A.G- Carmichael: "J. Econ. Entomol.", 44, page 317 (1961); B.
.Bchaerff enberg, E . Kupka: ",'Naturwissenschaften", 46, side 457 .Bchaerffenberg, E . Kupka: "'Naturwissenschaften'", 46, page 457
(1359)), altså som et stoff med motsatt biologisk virkning. (1359)), i.e. as a substance with the opposite biological effect.
Gjenstand for oppfinnelsen er således insektfrastøtende TTii fM-pT for kosmetiske eller tekniske formål, og midlene karak-teriseres ved et innhold på minst et (på nitrogenatomet disub-stituert) 3-aminopropionsyrederivat med den generelle formel T The object of the invention is thus insect repellent TTii fM-pT for cosmetic or technical purposes, and the agents are characterized by a content of at least one (disubstituted on the nitrogen atom) 3-aminopropionic acid derivative with the general formula T
der 1^ -betyr en rett eller forgrenet alkylrest med 1-6 kaxbon-atomex, R2 betyr et hydrogenatom eller en metylgruppe, :R3 betyr en-rett -eller f or grenet -alkyl gruppe med 1—8 karbonat omer eller en metoksy- eller etoksygruppe, og D.^ betyr en rett eller forgrenet alkylgruppe med 1—6 karbonatomer. where 1^ -means a straight or branched alkyl residue with 1-6 carbon atoms, R2 means a hydrogen atom or a methyl group, :R3 means a straight- or branched-alkyl group with 1-8 carbon atoms or a methoxy- or ethoxy group, and D.^ means a straight or branched alkyl group with 1-6 carbon atoms.
De insektfrastøtende midler ifølge oppfinnelsen, hvilke vanligvis, ved siden av vanlige tilsetnings- og/eller bærer-stoffer, inneholder minst en av de angitte på nitrogenatomet disubstituerte 3-aminopropionsyrederivater med formelen I, betyr et betydelig teknisk fremskritt. Dette gir seg av resultatene av sammenligningsforsøk som ble gjennomført med et middel ifølge oppfinnelsen, og som inneholdt 3-(N-n-butyl-N-acetyl)-aminopropionsyreetylester, sammenlignet med de kjente, godt virksomme handelspreparater dimetylftalat og m-toluylsyre-N,N-dietylamid (DEET), .hvorfra overlegenheten for midlene ifølge oppfinnelsen tydelig fremgår sammenlignet med forsøksstoffene. The insect repellents according to the invention, which usually, in addition to common additives and/or carriers, contain at least one of the 3-aminopropionic acid derivatives indicated on the nitrogen atom disubstituted with the formula I, represent a significant technical advance. This is based on the results of comparison tests that were carried out with an agent according to the invention, and which contained 3-(N-n-butyl-N-acetyl)-aminopropionic acid ethyl ester, compared to the known, well-effective commercial preparations dimethyl phthalate and m-toluic acid-N,N -diethylamide (DEET), from which the superiority of the agents according to the invention is clearly evident compared to the test substances.
A^. Prøving av den insektfrastøtende virkning (repellent-virkning) på Aédes aegypti 1. (stikkmygg). A^. Testing the insect repellent effect (repellent effect) on Aédes aegypti 1. (bite mosquito).
Fremgangsmåte: Underarmen til en forsøksperson tjener som mygglokkekilde- Den ble behandlet med en 5 vekt-%-ig opp-løsning av 3—(N-n-butyl—W-acetyl)-aminopropionsyreetylester i etanol ved jevn inngnidning. Forsøkspersonens hånd ble beskyttet Procedure: The forearm of a test subject serves as a source of mosquito bait - It was treated with a 5% by weight solution of 3-(N-n-butyl-W-acetyl)-aminopropionic acid ethyl ester in ethanol by uniform rubbing. The subject's hand was protected
i med en hanske. Den med det virksomme stoff behandlede underarm ble ført inn i et prøvebur med 500 sultne hunn—mygg. in with a glove. The forearm treated with the active substance was introduced into a test cage with 500 hungry female mosquitoes.
Resultat: I løpet av de foreskrevne 5 minutter ble det ikke bemerket hverken stikk eller at mygg nærmet seg den behandlede under arm. Result: During the prescribed 5 minutes, neither stings nor mosquitoes approaching the treated under arm were noted.
For å bestemme langtidsvirkningen for det virksomme stoff 3-(N-n-butyl-N-acetyl)-aminopropionsyreetylester ble det beskrevne forsøk gjentatt i avstander på 1 time. Derved ble for å sammen-ligne virksomheten for de kjente og gode insektfrastøtende stoffer: dimetylftalat og m-toluylsyre-N,N-dietylamid prøvet på samme måte. Ved siden av 3-(N-n—butyl-N-acetyl)-aminopropionsyreetylester To determine the long-term effect of the active substance 3-(N-n-butyl-N-acetyl)-aminopropionic acid ethyl ester, the described experiment was repeated at intervals of 1 hour. Thereby, in order to compare the activities of the known and good insect repellent substances: dimethyl phthalate and m-toluyl acid-N,N-diethylamide were tested in the same way. Next to 3-(N-n-butyl-N-acetyl)-aminopropionic acid ethyl ester
ble, som et videre middel, ifølge oppfinnelsen i denne langtids-prøving, også trukket inn: 3-(N-etyl-N-n-butyryl)-aminopropion-syremetylester. was, as a further agent, according to the invention in this long-term trial, also drawn in: 3-(N-ethyl-N-n-butyryl)-aminopropionic acid methyl ester.
Resultatet fremgår av følgende tabell: The result appears in the following table:
Sanmiehf atning: 1)" Ved anvendelse- av dimetylf talat avtok virkningen etter 3 timer; etter, utløp av denne tid (sammenlign 5-timers—verdien)', ble det bemerket tallrike stikk .og tallrike mygg som nærmet seg den behandlede underarm. 2) Ved anvendelse av 3— (N-n-butyl—N-acetyl)-aminopropionsyreetylester, 3-(N-etyl-N-n-butyryl)-amino-propionsyremetylester og m-toluylsyre-N,N-dietyl— amid kunne man heller ikke etter 5 timer bemerke at virkningen ga seg. Sanmiehf note: 1)" When using dimethyl phthalate, the effect decreased after 3 hours; after the expiration of this time (compare the 5-hour value)', numerous bites and numerous mosquitoes approaching the treated forearm were noted. 2) When using 3-(N-n-butyl-N-acetyl)-aminopropionic acid ethyl ester, 3-(N-ethyl-N-n-butyryl)-amino-propionic acid methyl ester and m-toluylic acid-N,N-diethyl- amide, one could also not after 5 hours note that the effect gave off.
A2- Prøving av den insektfrastøtende virkning (repellent virkning) på Anopheles albimanus (stikkmygg). fremgangsmåte: Som under A^. A2- Testing the insect repellent effect (repellent effect) on Anopheles albimanus (bite mosquito). procedure: As under A^.
Resultat: T løpet av den foreskrevne prøveperiode på 5 min. ble det ikke bemerket iverken mygg som nærmet seg, eller stikk på den, med de virksomme stoffer 3-(N-n-butyl-N-acetyl)— aminopropionsyreetylester og 3-(N-metyl— N-acetyl)-aminopropion-syre—n—butylester, behandlede underarm. Result: T during the prescribed trial period of 5 min. was not noted either mosquitoes approaching, or stinging it, with the active substances 3-(N-n-butyl-N-acetyl)- aminopropionic acid ethyl ester and 3-(N-methyl- N-acetyl)-aminopropionic acid—n —butyl ester, treated forearm.
Tm prøving av langtidsvirkningen under anvendelse av dimetylf talat og .m-toluylsyre~N,3Hdietyiamid, som sammelignings-stoffer, ga de -resultater, som er angitt i den følgende tabell: When testing the long-term effect using dimethyl phthalate and .m-toluylic acid~N,3Hdiethylamide, as comparative substances, they gave results, which are indicated in the following table:
Under hensyntagen til de store vanskeligheter som forelig-ger når man skal verge seg mot Anopheles—stikkmygg med repellen— ter (Åedes aegypti-stikkmygg er generelt adskillig lettere å på-virke ved repellenter), er den overlegenhet som fremgår av ta-bellen for midlene ifølge oppfinnelsen, sammenlignet med de kjente handelspreparater av spesiell betydning. Taking into account the great difficulties that exist when protecting against Anopheles mosquitoes with repellents (Åedes aegypti mosquitoes are generally much easier to affect with repellents), the superiority shown in the table for the agents according to the invention, compared to the known commercial preparations of special importance.
B. Prøving av slimhinnefordrageligheten. B. Mucosal tolerance testing.
Forsøksobjekt: Kaninøye. Test subject: Rabbit's eye.
Fremgangsmåten En dårpe av det virksomme stoff, som skal prøves, ble dryppet i bindehudsekken (tåresekken) i et kaninøye. Det andre øyet til kaninen (kontrollsiden) ble på samme måte behandlet med en dråpe fysiologisk koksaltoppiøsning. Etter en påvirkningstid på 1 min., ble de behandlede øyne spylt ut med håndvarmt vann. Bedømmelsen hhv. etterkontroll av kaninøynene skjedde i hvert tilfelle etter 1, 3, 24, 48 og 96 timer. 1 denne forsøksrekke ble det ved siden av 3—(N-n—butyl—N-acetyl)—aminopropionsyreetylester som sammenligningsstoff, anvendt dimetylftalat og m-toluylsyre-N,N-dietylamid. The procedure A drop of the active substance to be tested was dripped into the conjunctival sac (lacrimal sac) of a rabbit's eye. The other eye of the rabbit (control side) was similarly treated with a drop of physiological saline solution. After an exposure time of 1 min., the treated eyes were rinsed out with hand-warm water. The assessment or follow-up of the rabbit eyes occurred in each case after 1, 3, 24, 48 and 96 hours. In this series of experiments, in addition to 3-(N-n-butyl-N-acetyl)-aminopropionic acid ethyl ester as a comparison substance, dimethyl phthalate and m-toluylic acid-N,N-diethylamide were used.
Resultatet fremgår av følgende tabell: The result appears in the following table:
C. Prøving av innvirkningen på Jcunstoffgjenstander C. Testing of the impact on Jcunstoff articles
(oppløsnings— hhv. svelleevne). (dissolution or swelling ability).
Fremgangsmåte: En kulepenn av kunststoff og et 10 x 10 cm stort stykke av en kunststoff regnfrakk av myk PVC ble lagt 6 timer 1 en fortynnet (30 volum-%-ig etanol) 3— (N-n-butyl-N-acetyl)— aminopropionsyreetylester. Som s aTiimenll gni ngss tof f er ble det anvendt., 1 samme f oitynnelse, dimetylf talat og in-tolTiyl— syre-N, N-dietylami. d . Procedure: A plastic ballpoint pen and a 10 x 10 cm piece of a plastic raincoat made of soft PVC were placed for 6 hours in 1 diluted (30% by volume ethanol) 3— (N-n-butyl-N-acetyl)— aminopropionic acid ethyl ester . As usual, it was used at the same dilution, dimethyl phthalate and in-tolTiyl-acid-N,N-diethylami. d.
Resultat: 1) Ved anvendelse av .3— (N-n-butyl-N-acetyl)-aralnopropionsyreetylester viste de to kunststoffgjenstander ingen forandring av sin beskaffenhet. 2) Ved sammenligningsvirkestoffene m-toluylsyre-N,N-dietylamid og-dimetylftalat var begge kunstoffgjenstander an-grepet, overflatene var rå, klebrige og svellet. Result: 1) When using .3-(N-n-butyl-N-acetyl)-aralnopropionic acid ethyl ester, the two plastic objects showed no change in their nature. 2) With the comparative active substances m-toluyl acid-N,N-diethylamide and dimethyl phthalate, both plastic objects were attacked, the surfaces were raw, sticky and swollen.
t)e på nitrogenatomet di substituerte 3—aminopropionsyre-derivater med formelen 1, er delvis allerede kjente stoffer, delvis ennå ikke beskrevet i litteraturen. De kan fremstilles på i og for seg kjent måte, f.eks. ved addisjon av aminer med formel t)e on the nitrogen atom di substituted 3-aminopropionic acid derivatives with the formula 1, are partly already known substances, partly not yet described in the literature. They can be produced in a manner known per se, e.g. by addition of amines of formula
II II
på den reaktive C=C dobbeltbinding i akrylsyrederivater (hhv. 2-alkylakrylsyrederivater) med formelen 111der R^ i formel II samt R2 og R^ i formelen III har den ovenfor (i forbindelse med formel I) angitte betydning. Omsetningen av aminene med formel II med de, eventuelt i 2—stilling med en alkylrest substituerte, akrylsyrederivater med formelen II kan skje i nærvær eller fravær av fortynningsmidler, slik som alkoholer, alifatiske eller aromatiske hydrokarboner, hvorved man for å unngå dannelse av 2:l-addukter med formel V on the reactive C=C double bond in acrylic acid derivatives (respectively 2-alkylacrylic acid derivatives) with the formula 111where R^ in formula II as well as R2 and R^ in formula III have the meaning given above (in connection with formula I). The reaction of the amines of formula II with the acrylic acid derivatives of formula II, optionally substituted in the 2-position with an alkyl residue, can take place in the presence or absence of diluents, such as alcohols, aliphatic or aromatic hydrocarbons, whereby to avoid the formation of 2: l-adducts of formula V
må velge et molforhold på 2:1 mellom aminet II og akrylsyre-derivatet HI. must choose a molar ratio of 2:1 between the amine II and the acrylic acid derivative HI.
Denne addisjonsreaksjonen, som fører til forbindelser med formel VI altså til de på nitrogenatomet mono—substituerte 3—aminopropion— syrederivater, gjennomføres hensiktsmessig ved temperaturer mellom 0 og 100°C, fortrinnsvis i området mellom 5 og 30°C. This addition reaction, which leads to compounds of formula VI, i.e. to the 3-aminopropionic acid derivatives mono-substituted on the nitrogen atom, is conveniently carried out at temperatures between 0 and 100°C, preferably in the range between 5 and 30°C.
Reaksjonen kan gjennomføres ved vanlig trykk, ved anvendelse av ved romtemperatur meget flyktige aminer samt også for å akselerere reaksjonsforløpet også ved forhøyet trykk. Isoler-ingen og opparbeidingen av reaksjonsproduktene i henhold til formel IV skjer på vanlig måte ved destillasjon. The reaction can be carried out at normal pressure, by using amines that are very volatile at room temperature and also to accelerate the course of the reaction also at elevated pressure. The isolation and processing of the reaction products according to formula IV takes place in the usual way by distillation.
Disse, som mellomprodukter oppstående forbindelser ifølge IV, viser også en god insektfrastøtende virkning, men mindre utpreget og svakere enn ved de fra disse fremstil l ba re slutt— produkter med formelen I. De er dog av mindre kjemisk bestandig-het Dg således utbrukbare i praksis. These, as intermediates arising compounds according to IV, also show a good insect repellent effect, but less pronounced and weaker than in the case of the products with the formula I produced from these. practice.
Fremstillingen av sluttproduktene, de på nitrogenatomet disubsfituerte 3—aminopropionsyrederivater ifølge formel I, fra mellomproduktene ifølge formel IV, skjer i et etterfølgende reaksjonstrinn, ved omsetning av adduktene med formel TV med reaktive karboksylsyreklorider med formelen VI, hhv., med klor-maursyreestere med formel VII på i og for seg kjent måte: The preparation of the final products, the 3-aminopropionic acid derivatives disubstituted on the nitrogen atom according to formula I, from the intermediate products according to formula IV, takes place in a subsequent reaction step, by reacting the adducts of formula TV with reactive carboxylic acid chlorides of formula VI, respectively, with chloroformate esters of formula VII in a manner known per se:
hvorved R^ i formel "VI/VII har den ovenfor i forbindelse med formel I angitte betydning. whereby R^ in formula "VI/VII has the meaning given above in connection with formula I.
Denne omsetning skjer fordelaktig 1 narvar av tertiære nitrogenbaserT slik som trietylamin eller pyridin ved temperaturer mellom 0 og 30°C, hensiktsmessig under anvendelse av for— tynningsmidler.. Tortynningsmidler, som har vist seg egnet for dette formål, er aromatiske og alifatiske hydrokarboner. Reaksjonsproduktene med formelen I, som oppnås ved denne reaksjon, kan isoleres og renses på vanlig måte ved destillasjon.. This reaction takes place advantageously in the presence of tertiary nitrogen bases such as triethylamine or pyridine at temperatures between 0 and 30°C, suitably using diluents. Tort diluents, which have proven suitable for this purpose, are aromatic and aliphatic hydrocarbons. The reaction products with the formula I, which are obtained by this reaction, can be isolated and purified in the usual way by distillation.
Som eksempler på de ved den "beskrevne fremgangsmåte frem-stillbaré og ifølge, oppfinnelsen som insektfrastøtende middel anvendbare på nitrogenatomet disubstituerte 3-aminopropionsyrederivater, skal nevnes: As examples of the 3-aminopropionic acid derivatives that can be produced by the "described method and according to the invention as insect repellents usable on the nitrogen atom, the following should be mentioned:
De virksomme midler ifølge oppfinnelsen viser ved liten toksisitet overfor varmblodige dyr, en sterk insektfrastøtende virkning (xepellentvirknlng) overfor blodsugende insekter. Da virkningen varer lenge, kan disse midler anvendes i form av en for dette formål egnet tilberedning til vern mot skadelige blodsugende insekter- Disse midler er spesielt godt egnet til vern mot stikkmygg. The active agents according to the invention show, with little toxicity towards warm-blooded animals, a strong insect repellent effect (xepellent effect) towards blood-sucking insects. As the effect lasts for a long time, these agents can be used in the form of a preparation suitable for this purpose for protection against harmful blood-sucking insects - These agents are particularly well suited for protection against biting mosquitoes.
De virksomme midler innarbeides i de for repellenter vanlige salgbare former og kan anvendes i alle de i kosemetikkén vanlige anvendelsesformer, f.eks, i form av oppløsninger, emul-sjoner, salver, kremer, pulvere, pastaer, stifter eller spray, eller som aerosoler eller spraybokser. The active agents are incorporated in the marketable forms usual for repellents and can be used in all the usual forms of application in cosmetics, for example, in the form of solutions, emulsions, ointments, creams, powders, pastes, sticks or sprays, or as aerosols or spray cans.
Disse blir fremstilt på i og for seg kjent måte ved blanding eller fortynning av det virksomme stoff med oppløsningsmidler, tilsetningsstoffer og/ellex bærere, eventuelt under anvendelse av emulgatorer. These are prepared in a manner known per se by mixing or diluting the active substance with solvents, additives and/or carriers, possibly using emulsifiers.
De virksomme midler kan i disse tilberedninger foreligge som bl anrl- i ngs^pg+TiTifSrip-l , eventuelt også i blanding med andre virksomme stoffer, slik som f.eks. solbeskyttelsesmidler. The active agents can be present in these preparations as eg anrl-i ngs^pg+TiTifSrip-l , possibly also in a mixture with other active substances, such as e.g. sunscreens.
Tilberedningene inneholder vanligvis 0,1-95 vekt-% av det hhv. de virksomme stoffer, spesielt mellom 0,5 og 90 vekt-%. Fortrinnsvis bør dog andelen av det virksomme stoff i preparatet utgjøre 5-20 vekt-%. ' ' ... The preparations usually contain 0.1-95% by weight of the respective the active substances, especially between 0.5 and 90% by weight. Preferably, however, the proportion of the active substance in the preparation should amount to 5-20% by weight. ' ' ...
Til beskyttelse mot skadelige, blodsugende insekter kan For protection against harmful, blood-sucking insects can
de virksomme midler påføres menneske- eller dyréhud fortynnet eller ufortynnet i form av tilberedninger ved inngnidning eller spraying. En spesielt god virkning oppnås ved å anvende dem i form av alkoholisk-vandige preparater. Stoffene ifølge oppfinnelsen er videre egnet som tilsetning til impregneringsstoffer. for tekstilbaner, bekledningsgjenstander og forpakningsmateriale samt som tilsetning til polerings-, pusse-og vinduspussemidler.. the active agents are applied to human or animal skin diluted or undiluted in the form of preparations by rubbing in or spraying. A particularly good effect is achieved by using them in the form of alcoholic-aqueous preparations. The substances according to the invention are also suitable as an additive to impregnation substances. for textile tracks, upholstery items and packaging material as well as as an additive to polishing, polishing and window cleaning agents..
De følgende illustrerende eksempler skal. belyse oppfinnelsen nærmere. The following illustrative examples shall. explain the invention in more detail.
Eksempel 1 Example 1
5 g 3-(N-n-butyl-N-acetyl-aminopropionsyre-n-butylester 5 g of 3-(N-n-butyl-N-acetyl-aminopropionic acid-n-butyl ester).
5 g trioktanoin (forestringsproduktet, av glycerin og 3 5 g trioctanoin (the esterification product, of glycerin and 3
mol oktankarboksylsyre) moles of octanecarboxylic acid)
5 g 2-oktyldodekanol 5 g of 2-octyldodecanol
50 g isopropanol 50 g of isopropanol
10 g vann 10 g of water
blandes. Den herved oppnådde oppløsning er spesielt godt egnet til inngnidning og videre spesielt godt egnet som spraybart insekfrastøtende middel. mix. The solution thus obtained is particularly well suited for rubbing in and furthermore particularly well suited as a sprayable insect repellent.
Eksempel 2 Example 2
48 g kolloiddispergert blanding av 90 deler cetylstearyl-alkohol og 10 deler natriumcetylsteårylsulfat ("ian-ette N") 48 g colloidally dispersed mixture of 90 parts cetyl stearyl alcohol and 10 parts sodium cetyl stearyl sulfate ("ian-ette N")
24 g cetylalkohol .: 24 g cetyl alcohol.:
24 g mineralolje (viskositet ca. 3° Engler/50°C) 24 g mineral oil (viscosity approx. 3° Angels/50°C)
20 g 3-(N-n-butyl-N-acetyl)-aminopropipnsyreetylester blandes, og den oppnådde blanding oppvarmes til 70°C. En adskilt fra dette tilberedet og likeledes til. 70°C oppvarmet blanding av 240 g vann og 40 g glycerin tilsettes varmt (ved ca. 70~C) til den førstnevnte blanding under omrøring.. Under stadig omrøring oppstår det ved avkjøling en krem som egner seg som insektfra-støtende middel for inngnidning i huden. 20 g of 3-(N-n-butyl-N-acetyl)-aminopropionic acid ethyl ester are mixed, and the resulting mixture is heated to 70°C. A separate from this prepared and likewise to. 70°C heated mixture of 240 g of water and 40 g of glycerin is added hot (at approx. 70~C) to the first-mentioned mixture while stirring. With constant stirring, a cream is formed on cooling which is suitable as an insect repellent for rubbing in in the skin.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19722246433 DE2246433C3 (en) | 1972-09-21 | 1972-09-21 | Insect repellants |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| NO138429B true NO138429B (en) | 1978-05-29 |
| NO138429C NO138429C (en) | 1978-09-06 |
Family
ID=5857006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO367273A NO138429C (en) | 1972-09-21 | 1973-09-19 | INSECT REPRESENTATIVE. |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS538773B2 (en) |
| AT (1) | AT325342B (en) |
| CA (1) | CA1027475A (en) |
| CH (1) | CH581999A5 (en) |
| DE (1) | DE2246433C3 (en) |
| FI (1) | FI55600C (en) |
| NL (1) | NL175691C (en) |
| NO (1) | NO138429C (en) |
| SE (1) | SE391629B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3220885A1 (en) * | 1982-06-03 | 1983-12-08 | Bayer Ag, 5090 Leverkusen | INSECT DRIVER |
| DE3220884A1 (en) * | 1982-06-03 | 1983-12-08 | Bayer Ag, 5090 Leverkusen | INSECT DRIVER |
| FR2755141B1 (en) * | 1996-10-30 | 1999-01-29 | Johan A Benckiser Gmbh | INSECT REPELLENT COMPOSITION FOR SOLID SURFACE |
| DE19645920A1 (en) * | 1996-11-07 | 1998-05-14 | Merck Patent Gmbh | Stable formulation of an insect repellent |
| TWI225793B (en) * | 1997-12-25 | 2005-01-01 | Ajinomoto Kk | Cosmetic composition |
| GB9912560D0 (en) * | 1999-05-28 | 1999-07-28 | Bob Martin Company The | Ectoparasite control composition |
| AU1788202A (en) * | 2000-11-28 | 2002-06-11 | Avon Prod Inc | Anhydrous insect repellent composition |
| EP1421853A1 (en) * | 2002-11-23 | 2004-05-26 | Beiersdorf AG | Insect repellent composition |
| DE10349665A1 (en) * | 2003-10-24 | 2005-06-09 | Beiersdorf Ag | Insect repellent textile |
| DE102007026050A1 (en) | 2007-05-31 | 2008-12-04 | Beiersdorf Ag | Insect repellent and thickener |
| DE102007026053A1 (en) | 2007-05-31 | 2008-12-04 | Beiersdorf Ag | Insect repellent with good skin compatibility |
| DE102007026048A1 (en) | 2007-05-31 | 2008-12-04 | Beiersdorf Ag | Insect repellent and perfume |
| DE102007026052A1 (en) | 2007-05-31 | 2008-12-04 | Beiersdorf Ag | Insect repellents on an emulsion basis |
| DE102007026049A1 (en) | 2007-05-31 | 2008-12-04 | Beiersdorf Ag | Repellents against wasps |
| DE102007026051A1 (en) | 2007-05-31 | 2008-12-04 | Beiersdorf Ag | Insect repellent with reduced stickiness |
| DE102011015445A1 (en) | 2010-09-24 | 2012-03-29 | Alexander Wannenwetsch | Insect repellent, useful for the application in humans and animals, comprises amino acids comprising leucine and/or tryptophan |
| JP2012077091A (en) * | 2012-01-10 | 2012-04-19 | Earth Chemical Co Ltd | Aqueous pest-repelling composition |
-
1972
- 1972-09-21 DE DE19722246433 patent/DE2246433C3/en not_active Expired
-
1973
- 1973-09-18 AT AT804173A patent/AT325342B/en not_active IP Right Cessation
- 1973-09-19 JP JP10508473A patent/JPS538773B2/ja not_active Expired
- 1973-09-19 NL NL7312921A patent/NL175691C/en not_active IP Right Cessation
- 1973-09-19 NO NO367273A patent/NO138429C/en unknown
- 1973-09-20 CH CH1351573A patent/CH581999A5/xx not_active IP Right Cessation
- 1973-09-20 CA CA181,552A patent/CA1027475A/en not_active Expired
- 1973-09-20 FI FI293673A patent/FI55600C/en active
- 1973-09-20 SE SE7312833A patent/SE391629B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE2246433B2 (en) | 1974-08-08 |
| SE391629B (en) | 1977-02-28 |
| CH581999A5 (en) | 1976-11-30 |
| NL175691C (en) | 1984-12-17 |
| AT325342B (en) | 1975-10-10 |
| FI55600C (en) | 1979-09-10 |
| CA1027475A (en) | 1978-03-07 |
| JPS4969827A (en) | 1974-07-05 |
| NO138429C (en) | 1978-09-06 |
| NL7312921A (en) | 1974-03-25 |
| DE2246433A1 (en) | 1974-04-11 |
| NL175691B (en) | 1984-07-16 |
| FI55600B (en) | 1979-05-31 |
| DE2246433C3 (en) | 1975-03-27 |
| JPS538773B2 (en) | 1978-03-31 |
| AU6027573A (en) | 1975-03-13 |
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