TWI415827B - 製備２-胺基-５-氰基苯甲酸衍生物之方法 - Google Patents
製備２-胺基-５-氰基苯甲酸衍生物之方法 Download PDFInfo
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- TWI415827B TWI415827B TW096145457A TW96145457A TWI415827B TW I415827 B TWI415827 B TW I415827B TW 096145457 A TW096145457 A TW 096145457A TW 96145457 A TW96145457 A TW 96145457A TW I415827 B TWI415827 B TW I415827B
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- HQNZNIJPAYTWJK-UHFFFAOYSA-N 2-amino-5-cyanobenzoic acid Chemical class NC1=CC=C(C#N)C=C1C(O)=O HQNZNIJPAYTWJK-UHFFFAOYSA-N 0.000 title description 3
- 238000004519 manufacturing process Methods 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 218
- 150000001875 compounds Chemical class 0.000 claims abstract description 181
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 40
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 125000004186 cyclopropylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C1([H])[H] 0.000 claims abstract description 14
- 125000006450 cyclopropyl cyclopropyl group Chemical group 0.000 claims abstract description 12
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 125000006431 methyl cyclopropyl group Chemical group 0.000 claims abstract description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 243
- 238000002360 preparation method Methods 0.000 claims description 30
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 24
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical class [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 101100294106 Caenorhabditis elegans nhr-3 gene Proteins 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 71
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- 239000002585 base Substances 0.000 description 36
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- -1 3-substituted 2-amino-5-cyanobenzoic acid Chemical class 0.000 description 34
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- 239000012429 reaction media Substances 0.000 description 12
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 11
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 11
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- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 10
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 10
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- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 10
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
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- 239000007858 starting material Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- AWDBHOZBRXWRKS-UHFFFAOYSA-N tetrapotassium;iron(6+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+6].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] AWDBHOZBRXWRKS-UHFFFAOYSA-N 0.000 description 8
- UOCPQZOXOQZEGV-UHFFFAOYSA-N 2-amino-5-cyano-n,3-dimethylbenzamide Chemical compound CNC(=O)C1=CC(C#N)=CC(C)=C1N UOCPQZOXOQZEGV-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 7
- 239000011261 inert gas Substances 0.000 description 7
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 6
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
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- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
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- TXJUTRJFNRYTHH-UHFFFAOYSA-N 1h-3,1-benzoxazine-2,4-dione Chemical compound C1=CC=C2C(=O)OC(=O)NC2=C1 TXJUTRJFNRYTHH-UHFFFAOYSA-N 0.000 description 4
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- 238000001953 recrystallisation Methods 0.000 description 1
- IREVRWRNACELSM-UHFFFAOYSA-J ruthenium(4+);tetrachloride Chemical compound Cl[Ru](Cl)(Cl)Cl IREVRWRNACELSM-UHFFFAOYSA-J 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 description 1
- 235000012247 sodium ferrocyanide Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- DSLBDAPZIGYINM-UHFFFAOYSA-N sulfanium;chloride Chemical class S.Cl DSLBDAPZIGYINM-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- NVLRFXKSQQPKAD-UHFFFAOYSA-N tricarbon Chemical compound [C]=C=[C] NVLRFXKSQQPKAD-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/14—Preparation of carboxylic acid nitriles by reaction of cyanides with halogen-containing compounds with replacement of halogen atoms by cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
- C07C237/28—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton
- C07C237/30—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton having the nitrogen atom of the carboxamide group bound to hydrogen atoms or to acyclic carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Plural Heterocyclic Compounds (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US87639406P | 2006-12-21 | 2006-12-21 | |
| US90246507P | 2007-02-21 | 2007-02-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW200837040A TW200837040A (en) | 2008-09-16 |
| TWI415827B true TWI415827B (zh) | 2013-11-21 |
Family
ID=39277128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW096145457A TWI415827B (zh) | 2006-12-21 | 2007-11-29 | 製備２-胺基-５-氰基苯甲酸衍生物之方法 |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US8049029B2 (enExample) |
| EP (2) | EP2213654B1 (enExample) |
| JP (1) | JP5393476B2 (enExample) |
| KR (2) | KR101562070B1 (enExample) |
| CN (1) | CN101553460B (enExample) |
| AR (1) | AR064645A1 (enExample) |
| AU (1) | AU2007339307B2 (enExample) |
| BR (1) | BRPI0719473B8 (enExample) |
| CL (1) | CL2007003671A1 (enExample) |
| DK (1) | DK2213654T3 (enExample) |
| ES (1) | ES2450394T3 (enExample) |
| IL (1) | IL198388A (enExample) |
| PL (1) | PL2213654T3 (enExample) |
| TW (1) | TWI415827B (enExample) |
| WO (1) | WO2008082502A2 (enExample) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI432421B (zh) * | 2007-12-19 | 2014-04-01 | Du Pont | 製備２－胺基－５－氰基苯甲酸衍生物之方法 |
| TWI431000B (zh) | 2008-03-05 | 2014-03-21 | Du Pont | 製備２－胺基－５－氰基苯甲酸衍生物之方法 |
| BR112014000473B1 (pt) * | 2011-07-08 | 2020-04-14 | Bayer Ip Gmbh | processo para a preparação de 2-amino-5-ciano-n,3- dimetilbenzamida e compostos |
| CN109970707A (zh) | 2012-02-07 | 2019-07-05 | 拜耳知识产权有限责任公司 | 取代的邻氨基苯甲酸衍生物的制备方法 |
| TWI678354B (zh) | 2014-05-29 | 2019-12-01 | 新加坡商艾佛艾姆希農業新加坡有限公司 | 藉空氣氧化製備３-甲基-２-硝基苯甲酸之製程 |
| CN105523951A (zh) * | 2015-12-12 | 2016-04-27 | 常州大学 | 一种2-氨基-n，3-二甲基-4-氯-5-溴代苯甲酰胺的合成方法 |
| WO2019123194A1 (en) | 2017-12-20 | 2019-06-27 | Pi Industries Ltd. | Anthranilamides, their use as insecticide and processes for preparing the same. |
| BR112020012455B1 (pt) | 2017-12-20 | 2024-04-30 | Pi Industries Ltd | Pirazolopiridina-diamidas, seu uso como inseticida e processos para sua preparação |
| JP7307079B2 (ja) | 2018-01-30 | 2023-07-11 | ピーアイ インダストリーズ リミテッド | 新規アントラニルアミド、殺虫剤としてのその使用およびその製造方法 |
| CA3129876A1 (en) | 2019-02-18 | 2020-08-27 | Pi Industries Ltd. | A process for preparing anthranilic diamides and intermediates thereof |
| CN113614063A (zh) | 2019-02-22 | 2021-11-05 | Pi工业有限公司 | 合成氨茴二酰胺化合物及其中间体的方法 |
| TW202222162A (zh) | 2020-09-26 | 2022-06-16 | 印度商皮埃企業有限公司 | 鄰胺苯甲酸／醯胺化合物及其中間體的合成方法 |
| EP4380363A1 (en) | 2021-08-05 | 2024-06-12 | Syngenta Crop Protection AG | Method for controlling diamide resistant pests & compounds therefor |
| WO2024038436A1 (en) | 2022-08-16 | 2024-02-22 | Adama Makhteshim Ltd. | Process for preparing cyantraniliprole via amino-cyano-benzene derivative |
| WO2026047667A1 (en) | 2024-08-26 | 2026-03-05 | Adama Makhteshim Ltd. | Process for preparing amino-cyano-benzene derivatives |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040138468A1 (en) * | 2002-08-02 | 2004-07-15 | Buchwald Stephen L. | Copper-catalyzed formation of carbon-heteroatom and carbon-carbon bonds |
| US6867298B2 (en) * | 2001-04-24 | 2005-03-15 | Massachusetts Institute Of Technology | Copper-catalyzed formation of carbon-heteroatom and carbon-carbon bonds |
| WO2006062978A1 (en) * | 2004-12-07 | 2006-06-15 | E.I. Dupont De Nemours And Company | Method for preparing n-phenylpyrazole-1-carboxamides |
| WO2006068669A1 (en) * | 2004-07-26 | 2006-06-29 | E.I. Dupont De Nemours And Company | Mixtures of anthranilamide invertebrate pest control agents |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2023977A1 (en) * | 1989-09-27 | 1991-03-28 | Larry L. Filius | Anisole bromination |
| US6084136A (en) * | 1995-03-06 | 2000-07-04 | Albmarle Corporation | Process for the preparation of tetrabromobisphenol-A |
| JP4112000B2 (ja) * | 1995-03-06 | 2008-07-02 | アルベマール・コーポレーシヨン | テトラブロモビスフェノール−ａの製造方法 |
| HUP0000641A3 (en) | 1996-10-16 | 2001-02-28 | American Cyanamid Company Madi | Ortho-sulfonamido aryl hydroxamic acid derivatives, their use, as matrix metalloproteinase and tace inhibitors and pharmaceutical compositions containing them |
| ES2159488B1 (es) | 2000-03-07 | 2002-04-16 | Uriach & Cia Sa J | Procedimiento para la preparacion de derivados de pirimidona con actividad antifungica. |
| US6245950B1 (en) * | 2000-03-30 | 2001-06-12 | Council Of Scientific And Industrial Research | Process for the preparation of tetrabromobisphenol-A |
| TWI356822B (en) | 2001-08-13 | 2012-01-21 | Du Pont | Novel substituted dihydro 3-halo-1h-pyrazole-5-car |
| US7038057B2 (en) | 2001-08-13 | 2006-05-02 | E.I. Du Pont De Nemours And Company | Substituted 1H-dihydropyrazoles, their preparation and use |
| AR036872A1 (es) | 2001-08-13 | 2004-10-13 | Du Pont | Compuesto de antranilamida, composicion que lo comprende y metodo para controlar una plaga de invertebrados |
| TWI312274B (en) | 2001-08-13 | 2009-07-21 | Du Pont | Method for controlling particular insect pests by applying anthranilamide compounds |
| TWI343376B (en) | 2002-07-31 | 2011-06-11 | Du Pont | Method for preparing 3-halo-4, 5-dihydro-1h-pyrazoles |
| ES2424840T3 (es) | 2003-01-28 | 2013-10-09 | E.I. Du Pont De Nemours And Company | Insecticidas tipo ciano antranilamida |
| TWI367882B (en) | 2003-03-26 | 2012-07-11 | Du Pont | Preparation and use of 2-substituted-5-oxo-3-pyrazolidinecarboxylates |
| EP1789411A1 (en) | 2004-08-17 | 2007-05-30 | E.I. Dupont De Nemours And Company | Novel anthranilamides useful for controlling invertebrate pests |
| AU2005306363B2 (en) | 2004-11-18 | 2012-08-09 | E. I. Du Pont De Nemours And Company | Anthranilamide insecticides |
| TWI395728B (zh) * | 2006-12-06 | 2013-05-11 | Du Pont | 製備２-胺基-５-氰基苯甲酸衍生物之方法 |
-
2007
- 2007-11-29 TW TW096145457A patent/TWI415827B/zh active
- 2007-12-18 ES ES10002063.5T patent/ES2450394T3/es active Active
- 2007-12-18 PL PL10002063T patent/PL2213654T3/pl unknown
- 2007-12-18 EP EP10002063.5A patent/EP2213654B1/en active Active
- 2007-12-18 CL CL200703671A patent/CL2007003671A1/es unknown
- 2007-12-18 KR KR1020097015132A patent/KR101562070B1/ko active Active
- 2007-12-18 US US12/516,807 patent/US8049029B2/en active Active
- 2007-12-18 WO PCT/US2007/025800 patent/WO2008082502A2/en not_active Ceased
- 2007-12-18 AU AU2007339307A patent/AU2007339307B2/en active Active
- 2007-12-18 KR KR20157001936A patent/KR20150021585A/ko not_active Ceased
- 2007-12-18 CN CN2007800453902A patent/CN101553460B/zh active Active
- 2007-12-18 BR BRPI0719473A patent/BRPI0719473B8/pt active IP Right Grant
- 2007-12-18 EP EP07867794A patent/EP2094644A2/en not_active Withdrawn
- 2007-12-18 DK DK10002063.5T patent/DK2213654T3/da active
- 2007-12-18 JP JP2009542864A patent/JP5393476B2/ja active Active
- 2007-12-21 AR ARP070105813A patent/AR064645A1/es unknown
-
2009
- 2009-04-26 IL IL198388A patent/IL198388A/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6867298B2 (en) * | 2001-04-24 | 2005-03-15 | Massachusetts Institute Of Technology | Copper-catalyzed formation of carbon-heteroatom and carbon-carbon bonds |
| US20040138468A1 (en) * | 2002-08-02 | 2004-07-15 | Buchwald Stephen L. | Copper-catalyzed formation of carbon-heteroatom and carbon-carbon bonds |
| WO2006068669A1 (en) * | 2004-07-26 | 2006-06-29 | E.I. Dupont De Nemours And Company | Mixtures of anthranilamide invertebrate pest control agents |
| WO2006062978A1 (en) * | 2004-12-07 | 2006-06-15 | E.I. Dupont De Nemours And Company | Method for preparing n-phenylpyrazole-1-carboxamides |
Also Published As
| Publication number | Publication date |
|---|---|
| IL198388A0 (en) | 2010-02-17 |
| BRPI0719473B1 (pt) | 2021-06-29 |
| PL2213654T3 (pl) | 2014-06-30 |
| TW200837040A (en) | 2008-09-16 |
| EP2094644A2 (en) | 2009-09-02 |
| EP2213654B1 (en) | 2014-01-22 |
| ES2450394T3 (es) | 2014-03-24 |
| KR20090096632A (ko) | 2009-09-11 |
| KR101562070B1 (ko) | 2015-10-21 |
| JP2010513498A (ja) | 2010-04-30 |
| US8049029B2 (en) | 2011-11-01 |
| IL198388A (en) | 2014-06-30 |
| AU2007339307A1 (en) | 2008-07-10 |
| EP2213654A1 (en) | 2010-08-04 |
| BRPI0719473A2 (pt) | 2014-02-11 |
| AU2007339307B2 (en) | 2012-06-14 |
| JP5393476B2 (ja) | 2014-01-22 |
| AR064645A1 (es) | 2009-04-15 |
| KR20150021585A (ko) | 2015-03-02 |
| WO2008082502A3 (en) | 2008-10-16 |
| DK2213654T3 (da) | 2014-04-22 |
| WO2008082502A2 (en) | 2008-07-10 |
| CL2007003671A1 (es) | 2008-07-11 |
| BRPI0719473B8 (pt) | 2021-09-21 |
| US20100280251A1 (en) | 2010-11-04 |
| CN101553460B (zh) | 2013-09-04 |
| CN101553460A (zh) | 2009-10-07 |
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