TW200306977A - Preparation of 4-haloalkylnicotinamides - Google Patents
Preparation of 4-haloalkylnicotinamides Download PDFInfo
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- TW200306977A TW200306977A TW092113886A TW92113886A TW200306977A TW 200306977 A TW200306977 A TW 200306977A TW 092113886 A TW092113886 A TW 092113886A TW 92113886 A TW92113886 A TW 92113886A TW 200306977 A TW200306977 A TW 200306977A
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- 238000002360 preparation method Methods 0.000 title description 2
- 239000002253 acid Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 abstract description 14
- 238000007363 ring formation reaction Methods 0.000 abstract description 5
- 239000000575 pesticide Substances 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 150000002825 nitriles Chemical class 0.000 abstract description 3
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 abstract 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001409 amidines Chemical class 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- JUIWZYBJXUPIKF-UHFFFAOYSA-N 4-(trifluoromethyl)pyridine-3-carboxamide Chemical compound NC(=O)C1=CN=CC=C1C(F)(F)F JUIWZYBJXUPIKF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 125000004776 1-fluoroethyl group Chemical group [H]C([H])([H])C([H])(F)* 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- PNXJWEQRIVLWBG-UHFFFAOYSA-N 2-(trifluoromethyl)pyridine-3-carboxamide Chemical compound NC(=O)C1=CC=CN=C1C(F)(F)F PNXJWEQRIVLWBG-UHFFFAOYSA-N 0.000 description 1
- URYGFNNRWBURPO-UHFFFAOYSA-N 3-[(4,4,4-trifluoro-3-oxobut-1-enyl)amino]prop-2-enenitrile Chemical compound FC(F)(F)C(=O)C=CNC=CC#N URYGFNNRWBURPO-UHFFFAOYSA-N 0.000 description 1
- XPQPPDOZFFXVHN-UHFFFAOYSA-N 3-[(4,4-difluoro-3-oxobut-1-enyl)amino]prop-2-enenitrile Chemical compound FC(F)C(=O)C=CNC=CC#N XPQPPDOZFFXVHN-UHFFFAOYSA-N 0.000 description 1
- DHIRCRHQLUNYDS-UHFFFAOYSA-N 4-(trifluoromethyl)pyridine-3-carbonitrile Chemical compound FC(F)(F)C1=CC=NC=C1C#N DHIRCRHQLUNYDS-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 150000002081 enamines Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 235000005152 nicotinamide Nutrition 0.000 description 1
- 239000011570 nicotinamide Substances 0.000 description 1
- 229960003966 nicotinamide Drugs 0.000 description 1
- 150000005480 nicotinamides Chemical class 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- DFPAKSUCGFBDDF-UHFFFAOYSA-N nicotinic acid amide Natural products NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000006337 tetrafluoro ethyl group Chemical group 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
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
- C07D213/82—Amides; Imides in position 3
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
200306977 Π) 玖、發明說明 【發明所屬之技術領域】 本發明係關於製備4 -鹵院基蔽驗醯肖女之方法。 【先前技術】 4-鹵烷基菸鹼醯胺係作爲製備農藥的起始物，如〜〇· A 98/5 7 969、EP-A 0 5 80 374 及 WO-A 0 1/70692 中所述 者。 這些化合物可以兩階段自4-鹵烷基菸鹼酸製得，其合 成述於諸如EP_A 0 744 400中，或者藉4-鹵烷基菸鹼腈的 水解製得，可參考諸如WO-A 02/048 1 1 1。 現今意外發現製備4-鹵烷基菸鹼醯胺（特別是三氟甲 基菸鹼醯胺）的簡單方法，其係將3_(鹵烷基-3-酮基-1-丁 烯胺基）丙烯腈在強酸的存在下施以環化及水解作用。 【發明內容】 因此本發明提供製備式（1)之4 -鹵烷基菸鹼醯胺的方 法
其中，R1是（C1-C4)-鹵院基， 此方法包含將一或多個式（Π)、（ΙΠ)及/或（IV)的3-((C^CO-鹵院基-3-酮基-1-烯胺基）腈在強酸的存在下施以 閉環反應及水解作用 -4- (2) (2)200306977 R1-C(0)-CH = CH-NH-CH = CH-CN (Π) R】-C(〇）-CH = CH-NH-CH(ZR2)-CH2-CN (HI) R、C(〇）-CH = CH-NH-CH(Hal)-CH2-CN (IV) 其中 R1 定義如上； R2 可以相同或相異並且是烷基； Z 可以相同或相異並且是〇、S或NR1。 【實施方式】 依據本發明之方法可僅以一步驟自腈衍生物（II-IV)製 得菸鹼醯胺衍生物（I)並且特別容易操作。習知4-三氟甲 基菸鹼腈僅能在濃硫酸中及1 20至1 40 °C下加熱8小時方 得水解爲醯胺，就此而言，本發明特別出人意表。 (C1-C4)·鹵院基”是其中一或多個氫原子被等數目的相 同或相異之鹵原子（以氯或氟爲較佳）所取代的烷基，例 如三氟甲基、1-氟乙基、2,2,2-三氟乙基、氯甲基、氟甲 基、二氟甲基及1,1，2,2·四氟乙基。 式⑴至（IV)中的符號最好定義如下： R1 以 CF2H、CFC12、CF2Cb CF3、C2F5 或 C3F7 爲較 佳’以CF3爲更佳； R 2 以（c 1 · C4)-院基爲較佳，例如甲基、乙基、正丙 基、異丙基、正丁基、異丁基、第三丁基，並以甲基或乙 -5- (3) (3)200306977 基爲更佳，以甲基爲最佳； Z 以〇或NR1爲較佳；
Hal爲F、Cl、Br或I，以C1或Br爲較佳。 起始物3-(鹵烷基-3-酮基-1-烯胺基）丙烯腈衍生物（Π) 或者式（III)及（IV)的烯胺係已爲人知並且可以諸如WO-A 0 2/048 1 1 1中所述的方式製得。 轉化成4-鹵烷基菸鹼醯胺（I)的環化作用係於強酸的 存在下（pKa値以低於0.5爲較佳）發生。環化期間，CN 基團亦發生轉變。 最佳的酸是H2S〇4、SCh、發煙硫酸、磷酸、聚磷酸、 全氟烷磺酸，例如三氟甲磺酸、甲磺酸、及對位·甲苯磺 酸，並以H2S〇4及聚磷酸爲特佳，以H2S〇4爲極佳。 亦可以使用酸混合物。 化合物（II)、（III)及/或（IV)對酸的比率可以在寬廣範 圍內變化，視所用的化合物、酸及反應條件而定。 對每重量份的化合物（II)-(IV)而言，所用的酸量通常 爲4至30重量份，並以6至15重量份爲較佳。 反應溫度可在寬廣限値內變化，視所用的化合物及其 他反應條件而定。其通常在0°C至+40 °C的範圍內，且反 應時間通常爲0· 1至6小時，以3至5小時爲較佳。 反應條件亦以嫻於本技藝之人士所熟悉的方式變化， 視是否使用式（II)、（III)或（IV)之化合物而定。 反應可於溶劑中實施。組份（II-IV)及酸可在最初分別 載入溶劑中且該等溶液/懸浮液一起反應，或者可以先將 -6- (4) 200306977 組份之一載入溶劑中，再加入其他組份。 較佳的溶劑爲鹵化烴，例如二氯甲烷或氯仿，醚類， 例如乙醚或異丙醚，及S〇2。所用溶劑的量可在寬廣限値 內變化並且視諸如使用何種起始物而定。對每重量份的化 合物（II)-(IV)而言，溶劑的用量通常高至30重量份，並以 6至1 5重量份爲較佳。 此工作可藉嫻於本技藝之人士所習知的方法實施，例 如以水稀釋並將產物施以過濾或萃取。 水性混合對自其前驅物釋出醯胺及後續分離是極有必 要的，視環化劑（例如S〇3、發煙硫酸、濃H2S〇4 )的性 質而定。 化合物（I)(特別是4-三氟甲基菸鹼醯胺）可在穀物 保護劑（特別是農藥，例如殺蟲劑）之製備中作爲中間 物。 其特別適合進一步轉化成如WO-A 98/57969、EP-A 0 5 80 374及 WO-A 0 1/70692中所述的化合物。該等文件 (特別是各個例子及示範實施例中的式⑴化合物）係以參 考的方式倂於本文中；其係以參考的方式作爲此說明的一 部分。 本發明亦依據 WO-A 98/5 7969、EP-A 0 5 80 3 74 及/或 WO_A 0 1 /07692提供具殺蟲活性之鹵烷基菸鹼酸衍生物 (特別是4-三氟甲基菸鹼酸衍生物）的製法，此方法係先 製得上述的式（I)化合物，再將這些化合物施以閉環反應， 並視需要施以水解’再利用以上文件中所述及的方法將其 (5) (5)200306977 施以反應，即製得具有殺蟲活性的最終化合物°
German patent application 102 23 274.1 及其摘要之內 容係倂於本文中以爲參考。 本發明將利用以下實例作例舉說明，但是本1發明不爲 該等實例所限。 實例1 4-三氟甲基菸鹼醯胺 三頸瓶在氮氣下載入1〇〇毫升H2S〇4(d 1.8)，生成的 溶液冷卻至10°C。30克（0.5莫耳）的N“2-氰乙烯基）-4，4，4 -三氟-3 -酮基-卜丁烯胺在此溫度下於1小時內加入。 接著將混合物在室溫下（RT)攪拌3-5小時。將反應混合物 加至300克的冰中並以40重量％的NaOH將pH調整到3-4，產物以乙酸乙酯萃取。溶劑於減壓下去除。結果製得 27 克（90%)醯胺，熔點：1 66- 1 67 °C。19F NMR 5 : -60.0 (單峰）ppm。 實例2 4-三氟甲基菸鹼醯胺 重覆實例1之流程’但是此處以聚磷酸替代H2S〇4。 反應混合物加熱至4 0 °C並維持4小時’結果製得2 4克 (80%)產物，其熔點爲165°C。 (6) (6)200306977 4-二氟甲基菸鹼醯胺 重覆實例1之流程，但是此處以N-(2-氰乙烯基）-4,4-二氟-3-酮基丁烯胺替代N-(2-氰乙烯基）-4,4,4-三氟- 3-酮基-1-丁烯胺。產率65% ;熔點爲1 24- 1 25 1。
Claims (1)
- 200306977 Ο) 拾、申請專利範圍 1.一種製備式（1)之4-鹵烷基菸鹼醯胺的方法其中，R1是（C!-C4)__烷基， 此方法包含將一或多個式（II)、（III)及/或（IV)的3-((C^C%)-鹵烷基-3-酮基-1_烯胺基）腈在強酸的存在下施以 閉環反應及水解作用 R1-C(0)-CH = CH-NH-CH = CH-CN (Π) R1-C(0)-CH = CH-NH-CH(ZR2)-CH2-CN (Hi) Ri-C(〇）-CH = CH-NH-CH(Hal)-CH2-CN (IV) 其中 R1 定義如上； R2 可以相同或相異並且是（C!-^)·烷基； Z 可以相同或相異並且是0、S或NR1。 2·如申請專利範圍第1項之方法，其中式⑴中的Ri 是 CF2H、CFC12、CF2Cn、CF3、C2F5 或 C3F7。 3.如申請專利範圍第2項之方法，其中式⑴中的Rl 是 C F 3。 4 ·如申請專利範圍第1項之方法，其中該方法使用一 或多個選自H2S〇4、S〇3、發煙硫酸、磷酸、聚磷酸、全氟 烷磺酸、甲磺酸及對位-甲苯磺酸的酸。 (2) (2)200306977 5. 如申請專利範圍第4項之方法，其中該方法使用 H2S〇4 。 6. 如申請專利範圍第1項之方法，其中反應係於溶劑 中實施。-11 - 200306977 柒、（一）、本案指定代表圖為：第_圖 (二）、本代表圖之元件代表符號簡單說明： 無捌、本案若有化學式時，請揭示最能顯示發明特徵的化學 式··-3-
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10223274A DE10223274A1 (de) | 2002-05-24 | 2002-05-24 | Verfahren zur Herstellung von 4-Haloalkylnicotinsäureamiden |
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| Publication Number | Publication Date |
|---|---|
| TW200306977A true TW200306977A (en) | 2003-12-01 |
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| Application Number | Title | Priority Date | Filing Date |
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| TW092113886A TW200306977A (en) | 2002-05-24 | 2003-05-22 | Preparation of 4-haloalkylnicotinamides |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US7317105B2 (zh) |
| EP (1) | EP1511731A1 (zh) |
| JP (1) | JP2005535595A (zh) |
| KR (1) | KR20050004218A (zh) |
| CN (1) | CN1310888C (zh) |
| AU (1) | AU2003242532A1 (zh) |
| BR (1) | BR0311246A (zh) |
| DE (1) | DE10223274A1 (zh) |
| IL (1) | IL165356A0 (zh) |
| MX (1) | MXPA04011622A (zh) |
| TW (1) | TW200306977A (zh) |
| WO (1) | WO2003099791A1 (zh) |
| ZA (1) | ZA200408769B (zh) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113816901B (zh) * | 2021-08-27 | 2023-08-15 | 淮北龙溪生物科技有限公司 | 一种4－三氟甲基烟酰胺的合成方法 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2994182B2 (ja) | 1992-07-23 | 1999-12-27 | 石原産業株式会社 | アミド系化合物又はその塩、それらの製造方法及びそれらを含有する有害動物防除剤 |
| ATE443693T1 (de) * | 1995-05-26 | 2009-10-15 | Ishihara Sangyo Kaisha | Verfahren zur herstellung substituierter 1,1,1- trifluoro-3-buten-2-one |
| DE19725450A1 (de) * | 1997-06-16 | 1998-12-17 | Hoechst Schering Agrevo Gmbh | 4-Haloalkyl-3-heterocyclylpyridine und 4-Haloalkyl-5-heterocyclylpyrimidine, Verfahren zu ihrer Herstellung, sie enthaltende Mittel und ihre Verwendung als Schädlingsbekämpfungsmittel |
| CN1419542A (zh) * | 2000-03-22 | 2003-05-21 | 拜尔作物科学有限公司 | 杂环酰基硫酰亚胺化合物,其制法,含有其的组合物以及其作为杀虫之用途 |
| AR031658A1 (es) * | 2000-12-13 | 2003-09-24 | Aventis Cropscience Gmbh | Procedimiento para la preparacion de 4-haloalquilnicotinonitrilos |
| JPWO2003044013A1 (ja) | 2001-11-21 | 2005-03-10 | 三共アグロ株式会社 | Ｎ−ヘテロアリールニコチンアミド誘導体 |
-
2002
- 2002-05-24 DE DE10223274A patent/DE10223274A1/de not_active Withdrawn
-
2003
- 2003-05-09 JP JP2004507448A patent/JP2005535595A/ja active Pending
- 2003-05-09 CN CNB03811819XA patent/CN1310888C/zh not_active Expired - Fee Related
- 2003-05-09 IL IL16535603A patent/IL165356A0/xx unknown
- 2003-05-09 BR BR0311246-2A patent/BR0311246A/pt not_active IP Right Cessation
- 2003-05-09 MX MXPA04011622A patent/MXPA04011622A/es unknown
- 2003-05-09 KR KR10-2004-7018970A patent/KR20050004218A/ko not_active Ceased
- 2003-05-09 AU AU2003242532A patent/AU2003242532A1/en not_active Abandoned
- 2003-05-09 WO PCT/EP2003/004869 patent/WO2003099791A1/de not_active Ceased
- 2003-05-09 EP EP03755096A patent/EP1511731A1/de not_active Withdrawn
- 2003-05-09 US US10/515,507 patent/US7317105B2/en not_active Expired - Fee Related
- 2003-05-22 TW TW092113886A patent/TW200306977A/zh unknown
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2004
- 2004-10-29 ZA ZA2004/08769A patent/ZA200408769B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BR0311246A (pt) | 2005-03-15 |
| KR20050004218A (ko) | 2005-01-12 |
| ZA200408769B (en) | 2005-12-28 |
| MXPA04011622A (es) | 2005-03-07 |
| EP1511731A1 (de) | 2005-03-09 |
| US20060100217A9 (en) | 2006-05-11 |
| DE10223274A1 (de) | 2003-12-04 |
| CN1310888C (zh) | 2007-04-18 |
| JP2005535595A (ja) | 2005-11-24 |
| WO2003099791A1 (de) | 2003-12-04 |
| US7317105B2 (en) | 2008-01-08 |
| AU2003242532A1 (en) | 2003-12-12 |
| US20050176734A1 (en) | 2005-08-11 |
| IL165356A0 (en) | 2006-01-15 |
| CN1656074A (zh) | 2005-08-17 |
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