PL114067B1 - Process for preparing novel 2-/halogenalkoxyphenylo/-alkanocarbokxylic acids - Google Patents
Process for preparing novel 2-/halogenalkoxyphenylo/-alkanocarbokxylic acids Download PDFInfo
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- PL114067B1 PL114067B1 PL20119877A PL20119877A PL114067B1 PL 114067 B1 PL114067 B1 PL 114067B1 PL 20119877 A PL20119877 A PL 20119877A PL 20119877 A PL20119877 A PL 20119877A PL 114067 B1 PL114067 B1 PL 114067B1
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- Prior art keywords
- formula
- dioxane
- acids
- aqueous solution
- meta
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- 239000002253 acid Substances 0.000 title description 5
- 150000007513 acids Chemical class 0.000 title 1
- 238000004519 manufacturing process Methods 0.000 title 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- HYXJXCNHNYUWAZ-UHFFFAOYSA-N 2-methoxy-2-phenylacetonitrile Chemical compound COC(C#N)C1=CC=CC=C1 HYXJXCNHNYUWAZ-UHFFFAOYSA-N 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- -1 m-phenoxybenzyl compounds Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- ZCVAOQKBXKSDMS-AQYZNVCMSA-N (+)-trans-allethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OC1C(C)=C(CC=C)C(=O)C1 ZCVAOQKBXKSDMS-AQYZNVCMSA-N 0.000 description 1
- FMTFEIJHMMQUJI-NJAFHUGGSA-N 102130-98-3 Natural products CC=CCC1=C(C)[C@H](CC1=O)OC(=O)[C@@H]1[C@@H](C=C(C)C)C1(C)C FMTFEIJHMMQUJI-NJAFHUGGSA-N 0.000 description 1
- CNBUXJALZYSKQJ-UHFFFAOYSA-N 2-(4-methoxyphenyl)-3-methylbutanenitrile Chemical compound COC1=CC=C(C(C#N)C(C)C)C=C1 CNBUXJALZYSKQJ-UHFFFAOYSA-N 0.000 description 1
- LXJRCJQNKRXQLY-UHFFFAOYSA-N 2-[4-(difluoromethoxy)phenyl]pentanoic acid Chemical compound CCCC(C(O)=O)C1=CC=C(OC(F)F)C=C1 LXJRCJQNKRXQLY-UHFFFAOYSA-N 0.000 description 1
- 241000238876 Acari Species 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 229940024113 allethrin Drugs 0.000 description 1
- VEMKTZHHVJILDY-UXHICEINSA-N bioresmethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UXHICEINSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229960000490 permethrin Drugs 0.000 description 1
- RLLPVAHGXHCWKJ-UHFFFAOYSA-N permethrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 RLLPVAHGXHCWKJ-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
- A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
Przedmiotem wynalazku jest sposób wytwarza¬ nia nowych kwasów 2-(chlorowcoalkoksyfenylo)- -alkanokarboksylowych o wzorze ogólnym 3, w którym R oznacza grupe etylowa, n-propylowa lub izopropylowa a grupa dwufluorometoksylowa znajduje sie w polozeniu meta lub para uzytecz¬ nych do wytwarzania estrów m-fenoksybenzylo- wych wykazujacych dzialanie owadobójcze i roz- toczobójcze.Nieoczekiwanie stwierdzono, ze estry uzyskiwa¬ ne ze zwiazków wytwarzanych sposobem wedlug wynalazku sa nie tylko skutecznymi srodkami owadobójczymi lecz równiez bardzo skutecznymi srodkami kleszczobójczymi, a ponadto sa srodka¬ mi owadobójczymi i kleszczobójczymi o dzialaniu ukladowym. Zwiazki te posiadaja szeroki margi¬ nes bezpieczenstwa, wobec czego moga byc stoso¬ wane do skutecznej ochrony zwierzat domowych, laboratoryjnych i hodowlanych przed atakami owadów i kleszczy.Estry uzyskiwane ze zwiazków wytwarzanych sposobem wedlug wynalazku wykazuja lepsze re¬ sztkowe dzialanie kleszczobójcze i owadobójcze niz znane piretroidy takie jak permetryna, peno- tryna, aletryna itp., przy czym sa znacznie sku¬ teczniejsze w zwalczaniu moskitów.Wedlug wynalazku, zwiazki o ogólnym wzorze 3, w którym R oznacza grupe etylowa, n-propy¬ lowa lub izopropylowa wytwarza sie w ten spo¬ sób, ze odpowiedni alfa-alkilo meta- lub parame- toksyfenyloacetonitryl, poddaje sie reakcji ze ste¬ zonym kwasem bromowodorowym a nastepnie otrzymany produkt poddaje sie reakcji z chloro- dwufluorometanem w mieszaninie wodnego roz- 5 tworu alkalidów i dioksanu uzyskujac zadany kwas, jak to przedstawiono na zalaczonym na rysunku schemacie.Przyklad io Mieszanine 40,0 g a-izopropylo-4-metoksyfenylo- acetonitrylu i 200 ml 48% kwasu bromowodoro- wego ogrzewa sie pod chlodnica zwrotna w tem¬ peraturze 126—<128°C, na lazni olejowej, przez 14 godzin. Mieszanine reakcyjna rozciencza sie 15 lodem i woda, ekstrahuje kilkakrotnie eterem, przemywa woda i odparowuje do stalej pozosta¬ losci. Cialo stale gotuje sie z 200 ml chlorofor¬ mu, chlodzi, * filtruje i suszy. Wydajnosc 23,8 g, temperatura topnienia 172—174°C; ir(Nujol) 3250— 20 290 (szeroki, OH) 1690-1 (C=C).Porównywalne wyniki uzyskuje sie stosujac a-etylo-4-metoksyfenyloacetonitryl lub «-n-propy- lo-4-metoksyfenyloacetonitryl i uzyskujac kwas a-etylo-4-hydroksyfenylooctowy i kwas a-n-propy- 25 lo-4-hydroksyfenylooctowy.Do mieszanej mieszadlem magnetycznym mie¬ szaniny o temperaturze 80°C skladajacej sie z 10,000 g (0,0515 mola) kwasu a-izopropylo-4-hy- droksyfenylooctowego, 65 ml dioksanu, 19,08 g 30. (18,56 g rzeczywiste, 0,464 mola) wodorotlenku so- 114 0673 114 067 4 du i 30 ml wody wprowadza sie za pomoca bel- kotki 46 g (0,532 mola) chlorodwufluorometanu przez okres 4 godzin.Mieszanine reakcyjna wlewa sie do 250 ml wo¬ dy z lodem i otrzymana mieszanine przemywa eterem, zakwasza stezonym kwasem chlorowodo¬ rowym do pH = 3 i ekstrahuje 200 ml eteru. Roz¬ twór eterowy przemywa sie jednokrotnie 100 ml wody, suszy siarczanem sodu, filtruje i odparowuje uzyskujac biala paste. Dodaje sie mieszanine he¬ ksanu i chlorku metylenu i uzyskana mieszanine filtruje sie usuwajac czesci stale, które sa ma¬ terialem wyjsciowym. Filtrat odparowuje sie i uzyskuje sie 5,41 g klarownego, brazowego oleju.Oszacowuje sie w oparciu o NMR, ze produkt jest co najmniej o 85;% czystosci.NMR (CDC1 — d5 pirydyna) 8 7,43 (d,J = 8,2 H2l 2H), 8 7,03 (d, J3 = 8,2 H2, 2H), 8 6,57 (t. J = 74,3 H2, 1H), 8 3,63 (s,imp), 8 3,25 (d, J = 10 H2, 1H), <5 2,37 (m, 1H), 8 1,19 (d, J = 6,5 H2, 3H), 8 0,78 (d, J = 6,5 H2, 3H), 8 13,82 (s, 1H).Porównywalne wyniki uzyskuje sie stosujac kwas a-etylo-4-hydroksyfenylooctowy lub kwas «-n-propylo-4-hydroksyfenylooctowy uzyskujac kwas a-etylo-4-dwufluorometoksyfenylooctowy i 5 kwas a-n-propylo-4-dwufluorometoksyfenylooctowy odpowiednio.Zastrzezenie patentowe 10 Sposób wytwarzania nowych kwasów 2-(chlóro- wcoalkoksyfenylo)alkanokarboksylowych o ogól¬ nym wzorze 3, w którym R oznacza grupe ety¬ lowa, n-propylowa lub izopropylowa, a grupa dwu- fluorometoksylowa znajduje sie w polozeniu meta 15 lub para, znamienny tym, ze podstawiony w pozy¬ cji a odpowiednia grupa alkilowa meta lub para metoksyfenyloacetonitryl poddaje sie dzialaniu ste¬ zonego kwasu bromowodorowego, po czym uzy¬ skany produkt poddaje sie reakcji z chlorodwu- 20 fluorometanem w mieszaninie wodnego roztworu alkaliów i dioksanu.//.\N ch3o CH-CN I R 48 % HBr - /0-ch-co2h HO R WZÓR WZÓR 2 HO Dioksan €~^-CH-CClH + HCCIF ¦ A t.X—/ 1 2 ^^•"•'2 wodny roztwór R NaOH HCF20 Z O-CH-CO^ ,0 R WZÓR 2 WZÓR 3 SCHEMAT Cena 45 zl.Druk WZKart. 1-5023. PL PL PL PL PL PL PL The subject of the invention is a method for preparing new 2-(haloalkoxyphenyl)-alkanecarboxylic acids of the general formula 3, in which R is an ethyl, n-propyl or isopropyl group and the difluoromethoxy group is in the meta or para position useful for the preparation of esters. m-phenoxybenzyl compounds having insecticidal and acaricidal activity. Surprisingly, it was found that the esters obtained from the compounds prepared according to the invention are not only effective insecticides, but also very effective tickicides, and are also insecticides and tickicides with systemic action. These compounds have a wide margin of safety, so they can be used to effectively protect domestic, laboratory and farm animals against attacks by insects and ticks. Esters obtained from the compounds produced by the method according to the invention have better residual tickicidal and insecticidal effects than the known ones. pyrethroids such as permethrin, penothrin, allethrin, etc., and are much more effective in combating mosquitoes. According to the invention, compounds of the general formula 3, in which R is an ethyl, n-propyl or isopropyl group, are prepared in this method: the appropriate alpha-alkyl meta- or paramethoxyphenylacetonitrile is reacted with concentrated hydrobromic acid and then the obtained product is reacted with chlorodifluoromethane in a mixture of an aqueous solution of alkalides and dioxane to obtain the desired acid. , as shown in the attached diagram. Example io A mixture of 40.0 g of α-isopropyl-4-methoxyphenyl-acetonitrile and 200 ml of 48% hydrobromic acid is heated under reflux at a temperature of 126-<128°C , in an oil bath, for 14 hours. The reaction mixture is diluted with ice and water, extracted several times with ether, washed with water and evaporated to a solid. The solid is boiled with 200 ml of chloroform, cooled, filtered and dried. Yield 23.8 g, melting point 172-174°C; ir(Nujol) 3250— 20 290 (wide, OH) 1690-1 (C=C). Comparable results are obtained using a-ethyl-4-methoxyphenylacetonitrile or «-n-propyl-4-methoxyphenylacetonitrile and obtaining acid a -ethyl-4-hydroxyphenylacetic acid and a-n-propyl-4-hydroxyphenylacetic acid. To a mixture at 80°C, stirred with a magnetic stirrer, consisting of 10.000 g (0.0515 mol) of a-isopropyl-4-hy acid - droxyphenylacetic acid, 65 ml of dioxane, 19.08 g of 30. (18.56 g actual, 0.464 mol) sodium hydroxide - 114 0673 114 067 4 and 30 ml of water are introduced via a bubbler - 46 g (0.532 mol) of chlorodifluoromethane for a period of 4 hours. The reaction mixture is poured into 250 ml of ice water and the resulting mixture is washed with ether, acidified with concentrated hydrochloric acid to pH = 3 and extracted with 200 ml of ether. The ether solution is washed once with 100 ml of water, dried with sodium sulfate, filtered and evaporated to obtain a white paste. A mixture of hexane and methylene chloride is added and the resulting mixture is filtered to remove the solids that are the starting material. The filtrate is evaporated to give 5.41 g of a clear brown oil. The product is estimated to be at least 85% pure by NMR. NMR (CDC1 - d5 pyridine) 8 7.43 (d,J = 8 .2 H2l 2H), 8 7.03 (d, J3 = 8.2 H2, 2H), 8 6.57 (t. J = 74.3 H2, 1H), 8 3.63 (s,imp), 8 3.25 (d, J = 10 H2, 1H), <5 2.37 (m, 1H), 8 1.19 (d, J = 6.5 H2, 3H), 8 0.78 (d, J = 6.5 H2, 3H), 8 13.82 (s, 1H). Comparable results are obtained using a-ethyl-4-hydroxyphenylacetic acid or «-n-propyl-4-hydroxyphenylacetic acid, obtaining a-ethyl- 4-difluoromethoxyphenylacetic acid and α-n-propyl-4-difluoromethoxyphenylacetic acid, respectively. Patent claim 10. Method for preparing new 2-(haloalkoxyphenyl)alkanecarboxylic acids of the general formula 3, wherein R is an ethyl, n-propyl or isopropyl, and the difluoromethoxy group is in the meta or para position, characterized in that the meta or para alkyl group substituted in the a position is treated with concentrated hydrobromic acid, and then the obtained product is subjected to reaction with dichloromethane in a mixture of an aqueous solution of alkali and dioxane.//.\N ch3o CH-CN I R 48 % HBr - /0-ch-co2h HO R ¦ A t.X—/ 1 2 ^^•"•'2 aqueous solution R NaOH HCF20 Z O-CH-CO^,0 1-5023. PL PL PL PL PL PL PL
Claims (1)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US72881776A | 1976-10-01 | 1976-10-01 | |
| US72881876A | 1976-10-01 | 1976-10-01 | |
| US81460077A | 1977-07-11 | 1977-07-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| PL201198A1 PL201198A1 (en) | 1980-02-11 |
| PL114067B1 true PL114067B1 (en) | 1981-01-31 |
Family
ID=27419119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PL20119877A PL114067B1 (en) | 1976-10-01 | 1977-10-01 | Process for preparing novel 2-/halogenalkoxyphenylo/-alkanocarbokxylic acids |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JPS5344540A (en) |
| BG (2) | BG28238A3 (en) |
| BR (1) | BR7706474A (en) |
| CH (1) | CH638774A5 (en) |
| DE (1) | DE2743416A1 (en) |
| DK (1) | DK434777A (en) |
| GB (3) | GB1582775A (en) |
| GR (1) | GR72107B (en) |
| IL (1) | IL52973A (en) |
| PL (1) | PL114067B1 (en) |
| SU (1) | SU1082782A1 (en) |
| TR (1) | TR22094A (en) |
| YU (1) | YU40906B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GR74446B (en) * | 1978-03-20 | 1984-06-28 | American Cyanamid Co | |
| DE2837524A1 (en) * | 1978-08-28 | 1980-03-20 | Bayer Ag | Phenylacetic acid ester derivs. from pyrethroid alcohol(s) - useful as insecticides and acaricides, and new intermediates |
| US4284643A (en) * | 1978-08-28 | 1981-08-18 | Bayer Aktiengesellschaft | Combating arthropods with novel fluorine-containing phenylacetic acid esters |
| JPS56133253A (en) * | 1980-03-24 | 1981-10-19 | Sumitomo Chem Co Ltd | Optical isomer of cyanohydrin ester, its production and insecticide and acaricide containing the same as effective ingredient |
| JPS60174599U (en) * | 1984-04-27 | 1985-11-19 | 横河電機株式会社 | Crystal can automatic brewing device |
| JPH04720Y2 (en) * | 1984-10-24 | 1992-01-10 | ||
| JPS6174399U (en) * | 1984-10-24 | 1986-05-20 | ||
| DE102006023413A1 (en) * | 2006-05-17 | 2007-11-22 | Bayer Cropscience Ag | Soaked with insecticidal paper |
-
1977
- 1977-09-21 IL IL5297377A patent/IL52973A/en unknown
- 1977-09-26 GB GB4004377A patent/GB1582775A/en not_active Expired
- 1977-09-26 GB GB2486678A patent/GB1604875A/en not_active Expired
- 1977-09-27 DE DE19772743416 patent/DE2743416A1/en active Pending
- 1977-09-27 TR TR2209477A patent/TR22094A/en unknown
- 1977-09-28 BR BR7706474A patent/BR7706474A/en unknown
- 1977-09-28 GR GR54449A patent/GR72107B/el unknown
- 1977-09-30 BG BG3746777A patent/BG28238A3/en unknown
- 1977-09-30 BG BG7741086A patent/BG28695A4/en unknown
- 1977-09-30 YU YU233577A patent/YU40906B/en unknown
- 1977-09-30 CH CH1199877A patent/CH638774A5/en not_active IP Right Cessation
- 1977-09-30 DK DK434777A patent/DK434777A/en unknown
- 1977-10-01 PL PL20119877A patent/PL114067B1/en unknown
- 1977-10-01 JP JP11733977A patent/JPS5344540A/en active Pending
-
1978
- 1978-05-23 GB GB2166078A patent/GB1596903A/en not_active Expired
- 1978-10-12 SU SU782672702A patent/SU1082782A1/en active
Also Published As
| Publication number | Publication date |
|---|---|
| BG28238A3 (en) | 1980-03-25 |
| GB1582775A (en) | 1981-01-14 |
| IL52973A (en) | 1983-10-31 |
| PL201198A1 (en) | 1980-02-11 |
| BG28695A4 (en) | 1980-06-16 |
| JPS5344540A (en) | 1978-04-21 |
| GB1596903A (en) | 1981-09-03 |
| DK434777A (en) | 1978-04-02 |
| TR22094A (en) | 1986-04-02 |
| YU233577A (en) | 1983-02-28 |
| SU1082782A1 (en) | 1984-03-30 |
| GR72107B (en) | 1983-09-14 |
| DE2743416A1 (en) | 1978-04-06 |
| GB1604875A (en) | 1981-12-16 |
| BR7706474A (en) | 1978-06-06 |
| CH638774A5 (en) | 1983-10-14 |
| YU40906B (en) | 1986-08-31 |
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